MULTI-LAYER STRUCTURE, AND METHOD FOR YOUR PRODUCTION

专利摘要:
multilayer structure and method for producing it. A multilayer structure comprising no less than 8 resin layers, the resin layer including a layer consisting of a gas barrier resin-containing resin composition, and a layer b consisting of a resin-containing resin composition is described. a thermoplastic resin, at least one of the resin compositions included in layer a and layer b, which are adjacent to each other, containing a metal salt, the content of the metal salt being no less than 1 ppm and no more than 10,000 ppm in terms of equivalent metal element, and an adhesive interlayer force between layer a and layer b being no less than 450 g / 15mm. layer a and layer b may be alternately laminated. Moreover, the average single layer thickness of at least one selected from layer a and layer b is preferably not less than 0.01? and not more than 10?.
公开号:BR112012013271B1
申请号:R112012013271-7
申请日:2010-11-30
公开日:2019-09-17
发明作者:Shinji Tai；Hiroshi Kawai；Satoshi Yamakoshi；Kouta Isoyama；Masao Hikasa；Kentaro Yoshida
申请人:Kuraray Co., Ltd.；
IPC主号:

专利说明:

Descriptive Report of the Invention Patent for MULTILAYER STRUCTURE, AND METHOD FOR ITS PRODUCTION. Technical Field [001] The present invention relates to a multilayer structure which includes no less than 8 layers of resin, and method for producing the same and more particularly it relates to a multilayer structure having superior gas barrier properties, elasticity, thermoformability and durability and being excellent in adhesion between layers, and a method to produce the same.
Background of the Technique [002] Today, laminated films featuring a layer of ethylene-vinyl alcohol copolymer have been used in applications such as food packaging materials and medical applications, taking advantage of their superior gas barrier properties, elasticity and thermoformability and the like. Recently, in order to improve various types of performance, such as gas barrier properties, several multilayer structures have been proposed in which a plurality of resin layers are laminated, each layer having a thickness of micron or submicron order.
[003] Conventional multilayer structures developed so far, in which a plurality of resin layers of an ethylene-vinyl alcohol copolymer which are laminated, include, for example: (1) an elastomeric barrier film in which at least ten layers of a microlayer polymer compound formed from a fluid barrier material, such as an ethylene vinyl alcohol copolymer, and an elastomer material, such as thermoplastic polyurethane, are alternately laminated (see Unexamined Japanese Patent Application (Translation PCT Application), Publication No.
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2.002-524.317), (2) alternating multilayer film including layers of a rigid polymer material, such as a copolymer of ethylene vinyl alcohol and flexible polymer material (see Unexamined Japanese Patent Application (PCT Application Translation), Publication No. 2.003-512.201), and the like.
[004] However, according to the conventional multilayer structure mentioned above (1), the adhesiveness between a fluid barrier material, such as an ethylene vinyl alcohol copolymer and an elastomer material, such as thermoplastic polyurethane is not of any kind. considered. In addition, also according to the conventional multilayer structure mentioned above (2), the rigid polymer material per se, such as a copolymer of ethylene vinyl alcohol, and the combination thereof with the flexible polymer material, and the like are not investigated in connection with the adhesiveness of between layers, but only one technique of reinforcing the adhesiveness between each layer, using an adhesion layer merely consisting of a hot melt adhesive is described. Thus, according to these conventional multilayer structures (1) and multilayer structure (2), the adhesiveness between layers is insufficient and, due to the delamination between the layers and the like, cracks are likely to be generated in the barrier layer, in this way the durability can be deteriorated. As a result, in the conventional multilayer structure (1) the gas barrier properties may be insufficient for use in food packaging and the like. Prior art documents
Patent Documents [005] Patent Document 1: Japanese Patent Application No
Examined (PCT Application Translation), Publication No. 2002-524317 [006] Patent Document 2: Japanese Patent Application No
Examined (PCT Request Translation), Publication No. 2003-512201
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SUMMARY OF THE INVENTION
Problems to be solved by the invention [007] The present invention was made showing these disadvantages, and an objective of the invention is to provide multilayer structure which is excellent in adhesiveness between layers, has superior properties of gas barrier, elasticity, thermoformability and the like , and is capable of maintaining characteristics such as gas barrier properties, even when used with deformation, such as stretching or bending imposed. In addition, another object of the invention is to provide a method for producing a multilayer structure having such characteristics, while avoiding an increase in production costs.
Means to solve the problems [008] As an aspect of the invention made to solve the previous problems is the multilayer structure that includes not less than 8 layers of resin, the layer of resin including a layer A consisting of a resin composition containing a resin of gas barrier, and a layer B consisting of a resin composition containing a thermoplastic resin, at least one of the resin compositions included in layer A and layer B which are adjacent to each other containing a metal salt, the salt content of metal being not less than 1 ppm and not more than 10,000 ppm, in terms of equivalent metal element, and an adhesive strength between layers between layer A and layer B being not less than 450 g / 15 mm.
[009] The multilayer structure has superior gas barrier properties, elasticity and thermoformability due to the inclusion of no less than 8 layers of resin. In addition, due to: include a layer A, containing a gas barrier resin, and a layer B containing thermoplastic resin, at least one of the resin compositions included in layer A and layer B, which are ad
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4/158 lying with each other containing a metal salt; and the adhesive strength between layers between layer A and layer B is not less than 450 g / 15 mm, the structure and multilayer has much higher adhesive between layers. In this way, due to the very superior adhesion between layers, the multilayer structure maintains characteristics such as the superior gas barrier properties even against deformations such as elongation or bending, and has a very high durability.
[0010] Layer A and Layer B can be laminated alternately. By thereby alternately laminating layer A and layer B, each interlayer formed by lamination can achieve the above-mentioned upper adhesion. As a result, the adhesion between layers of the multilayer structure, in turn, gas barrier properties, durability, and the like can be significantly improved.
[0011] The average single layer thickness of at least one selected from layer A and layer B is preferably not less than 0.01 pm and not more than 10 pm. When the average thickness of layer A and / or layer B is within the above range, the number of layers can be increased, even if the entire multilayer structure has an identical thickness and, consequently, the gas barrier properties, durability and similar to the multilayer structure can be further improved.
[0012] The multilayer structure preferably has a thickness of not less than 0.1 pm and not more than 1000 pm. When the multilayer structure has a thickness within the above range, along with the effects achieved by the average thickness of layer A and / or layer B within the range, as described above, the gas barrier, durability, elasticity and similar properties can be further improved, while maintaining applicability
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5/158 for food packaging materials and the like.
[0013] As the metal salt, at least one selected from the group consisting of alkali metal salts, alkaline earth metal salts and Group D metal salts from Group 4 of the periodic table can be used. When such a metal salt is used, the adhesion between layers between layer A and layer B can be effectively achieved, and as a result, the gas barrier, durability and similar properties of the multilayer structure can be further improved.
[0014] The gas barrier resin can be a copolymer of ethylene-vinyl alcohol. The use of the ethylene vinyl alcohol copolymer as a gas barrier resin allows the gas barrier properties of the multilayer structure to be further improved.
[0015] The ethylene content of ethylene-vinyl alcohol copolymer units is preferably not less than 3 mol% and not more than 70 mol%. When the content of ethylene units falls within the above range, the gas barrier properties of the multilayer structure are improved, and in addition, the melt formability can be improved, so that improved adhesion between layers is allowed due to the superior fusion formability.
[0016] The ethylene vinyl alcohol copolymer preferably has a degree of saponification of not less than 80 mol%. When the degree of saponification is within the above range, the gas barrier properties of the multilayer structure can be further improved, and the resistance to moisture can also be improved. In addition, the degree of saponification falling within the above range serves to allow the adhesion between layers with layer B to be improved.
[0017] It is desired that the ethylene-vinyl alcohol copolymer in
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6/158 includes at least one selected from the group consisting of the following structural units (I) and (II), and [0018] The content of at least one selected of the structural units (I) or (II) with respect to the structural units whole is not less than 0.5 mol% and not more than 30 mol%.
- ch ₂ ch -
R ¹ - C - R ³ (I) l ₂
R ² - CH ₂ CH -
I _R ._k.
I
R ⁵ —C —R ⁷
I
OH [0019] in Formula (I) above, R ¹ , R ² and R ³ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms carbon, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a hydroxyl group; two between R ¹ , R ² and R ³ can bond with each other, unless the two between R ¹ , R ² and R ³ both represent a hydrogen atom; and the aliphatic hydrocarbon group having 1 to 10 carbon atoms, the alicyclic hydrocarbon group having 3 to 10 carbon atoms and the aromatic hydrocarbon group having 6 to 10 carbon atoms can have a hydroxyl group, a carboxyl group or an atom halogen; and [0020] in Formula (II) above, R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a hydrocarbone group
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7/158 aliphatic having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a hydroxyl group; R ⁴ and R ⁵ or R ⁶ and R ⁷ can bond with each other, unless both R ⁴ and R ⁵ , or both R ⁶ and R ⁷ represent a hydrogen atom, the aliphatic hydrocarbon group having 1 at 10 carbon atoms, the alicyclic hydrocarbon group having 3 to 10 carbon atoms and the aromatic hydrocarbon group having 6 to 10 carbon atoms can have a hydroxyl group, an alkoxy group, a carboxyl group or a halogen atom.
[0021] When the ethylene-vinyl alcohol copolymer of layer A thus includes the structural unit (I) and / or a content within the aforementioned position, characteristics of flexibility and processing of the resin composition that constitutes the layer A are improved, and in this way the adhesiveness, elasticity and thermoformability of the multilayer structure can be improved.
[0022] The layer A resin composition may contain a phosphate compound in an amount of not less than 1 ppm and not more than 10,000 ppm, in terms of phosphoric acid group equivalent, a carboxylic acid in an amount of not less than 1 ppm and not more than 10,000 ppm, or a boron compound in an amount of not less than 1 ppm and not more than 2,000 ppm in terms of boron equivalent. By thus containing a phosphate compound, a carboxylic acid or a boron compound in the layer A resin composition, the thermal stability of the multilayer structure in melting formation can be improved and, consequently, the adhesiveness between layers of the multilayer structure can be improved.
[0023] It is desired that the thermoplastic resin be at least sePetition 870190056670, of 19/06/2019, p. 11/172
8/158 taught from the group consisting of thermoplastic polyurethane, polyamide, and an adhesive resin presenting a functional group capable of reacting with a group included in the gas barrier resin in the molecule. According to the multilayer structure, as long as the aforementioned resin is used as a thermoplastic resin, the adhesiveness between layers and the like can be further improved.
[0024] It is desired that the thermoplastic resin include the adhesive resin having a functional group capable of reacting with a group included in the gas barrier resin in the molecule, wherein the adhesive resin is at least one resin selected from the group consisting of modified polyolefin. by carboxylic acid and a metal salt thereof, a thermoplastic resin having a boron-containing group capable of being converted into a boronic acid in the presence of a group of boronic acid or water, and a copolymer-based vinyl ester. When the adhesive resin mentioned above is used, the adhesiveness between layers between layer A and layer B is further improved. In this way, the multilayer structure allows the properties, durability and the like of the gas barrier to be further improved [0025] It is desired that the resin composition that constitutes layer A and / or layer B has a melting viscosity (ιγ) as determined at a temperature of 210 ° C and a shear rate of 10 / s being not less than 1 x 10 ² Pa · S and not more than 1 x 10 ⁴ Pa s · and a melting viscosity (12) as determined at a temperature of 210 ° C and a shear rate of 1,000 / s being not less than 1 x 10 ¹ Pa · s and not more than 1 x 10 ³ Pa · s, and a proportion (12/11) of the melt viscosity satisfies the Formula (1) to follow.
-0.8 <(1/2) log. (11/12) <-o.1 (1).
[0026] When the resin composition of layer A and / or layer
B, in this way, presents a melting viscosity and a proportion
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9/158 melt viscosity fits in the above range, layer A and layer B, in turn, the multilayer structure can be formed with a size as desired, and at a high speed, and an effect of improving adhesiveness between layers is also displayed.
[0027] A ratio (| 2b / | 2a) of a melt viscosity (| 2b) of the layer B resin composition to a melt viscosity (| 2a) of the layer A resin composition, as determined at a temperature 210 ° C and the shear rate of 1000 / s is preferably 0.3 or greater and 2 or less. When the proportion (| 2b / | 2a) of the melt viscosity fits DNA above the band, an adhesive force between layer A and layer B, in a multilayer structure obtained by the formation of melt can be further enhanced, and the durability of multilayer structure can be improved.
[0028] Furthermore, it is also preferred that at a temperature higher than a Vicat softening temperature of the resin composition that constitutes layer A or layer B by 30 ° C, the resin composition of layer A and / or layer B has a melting viscosity (| 2 ') as determined at a shear rate of 10 / s being not less than 1x 10 ² Pa. if not more than 1x10 ⁴ Pa. if a melting viscosity {| 2 '} as determined at a shear rate of 1,000 / s being not less than 1 x 10' Pa. if not more than 1 x 10 'Pa. s, and that a proportion (r '| 2') of the melt viscosity satisfies the following Formula (1 '):
-0.8 <(1/2) log. (η '/ η) <-0.1 (1').
[0029] Therefore, also when the composition of layer A resin in this way has a melt viscosity and a melt viscosity ratio that fits in the above ratio, layer A and layer B, in turn, the structure multilayer can be formed with a size as desired and at a high speed, and an effect of improving adhesiveness among
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[0030] Furthermore, at a temperature higher than the Vicat softening temperature of the layer A resin composition by 30 ° C, a proportion (η '/ η') of a melting viscosity (η ') of the layer B resin composition for a melt viscosity (η ') of the layer A resin composition, as determined at a shear rate of 1,000 / s, is preferably 0.3 or more and 3 or less. When the proportion (η '/ η') of the melt viscosity falls in the above range, the adhesive force between layer A and layer B, in a multilayer structure obtained by the formation of melt, as it is still intensified, and the durability multilayer structure can be further improved.
[0031] In a multilayer structure, it is preferable that a bonding reaction takes place at an interface between layer A and layer B. Thus, through bonding by means of a covalent bond or ionic bond between the molecules of the resin compositions that constitute layer A and layer B, more adhesion between upper layers can be achieved. As a result, the gas barrier, durability and similar properties of the multilayer structure can be further improved.
[0032] The multilayer structure is appropriately used for food packaging. It is necessary that the packaging materials used for food packaging, etc. maintain superior barrier properties while repeatedly subjected to deformation such as elasticity or flexion during use, and thus, the multilayer structure having characteristics such as superior gas barrier properties, durability and flexibility as described above, can be used appropriately.
[0033] In addition, another aspect of the present invention made to solve the previous problems provides a method for the production of
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11/158 multilayer structure, the method including formation through a multilayer coextrusion process using a resin composition containing a thermoplastic resin. According to the method for producing multilayer structure, the multilayer structure which is excellent in adhesiveness between layers, and has superior gas barrier properties, elasticity and durability can be produced easily and, certainly, while avoiding an increase in production costs.
Effects of the Invention [0034] As explained in the previous one, since the multilayer structure of the present invention is excellent in interlayer adhesiveness, it presents not only superior gas barrier properties, as well as elasticity and thermoformability in combination, but also superior durability of such that features such as upper gas barrier properties can be maintained, even in the case where it is used with deformation, such as stretching or bending imposed in use for food packaging material and the like. In addition, according to the method for producing multilayer structure of the present invention, multilayer structure having such characteristics can be produced easily and, certainly, while suppressing the increase in production costs. Description of embodiments [0035] Hereinafter, embodiments of the present invention are described in detail.
[0036] The multilayer structure includes not less than 8 layers of resin. The resin layer includes a layer A made up of a resin composition containing a gas barrier resin, and a layer B made up of a resin composition containing a thermoplastic resin. In layer A and layer B, at least one of the resin compositions included in layer A and layer B, which
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[0037] Hereinafter, a layered structure, layer A, layer B, metal salt, the relationship between layer A and layer B and a method of producing the multilayer structure are explained in this order.
Layered structure of the multilayered structure [0038] The multilayered structure includes not less than 8 layers of resin. Due to the configuration in which not less than 8 layers of resin are laminated, the continuous development of defects such as microporosity and disruption can be avoided, and as a result, the multilayer structure has superior characteristics, such as gas barrier properties and resulting durability from the structure per se. In this regard, and in light of the production, the total number of resin layers is particularly preferable not less than 10, more preferably not less than 15, and particularly preferable not less than 18.
[0039] The resin layer includes at least two types of layers, layer A and layer B, and another layer C and the like can be included. Laminating at least 8 layers in total of two or more types of layers, including layer A made up of a resin composition containing a gas barrier resin and layer B made up of a resin composition containing a thermoplastic resin, a multilayer structure showing superior gas barrier properties resulting from layer A, and elasticity and thermoformability resulting from layer B in combination can be provided. In addition, the multilayer structure can maintain the gas barrier properties, even if used with repeated deformation, such as stretching or imposed bending, due to the laminated configuration of layer A and layer B.
[0040] It should be noted that layer A can be constituted
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[0041] The laminating order of layer A and layer B is not particularly limited, whereas a structure having at least one location including layer A and layer B being adjacent to each other is formed. For example, rolling orders, such as:
(1) A, B, A, B ... A, B (that is, (AB) n);
(2) A, B, A, B ... A (that is, (AB) nA);
(3) B, A, B, A ... B (i.e., (BA) nB); and (4) A, A, B, B ... B, B (ie (AABB) n) [0042] can be employed. In addition, when layer C is included, for example, the lamination order such as (5) A, B, C ... A, B, C (i.e., (ABC) n) [0043] can be employed.
[0044] In particular, according to preferred lamination orders of layer A and layer B, layer A and layer B are alternately laminated as in the above (1), (2) or (3). Thus, the alternately laminated structure makes the multilayer structure have superior gas barrier properties and flexibility. In addition, strong adhesive force between layer A and layer B described later can be affected in the entire interlayer, where defects such as interlayer delamination can be significantly reduced. As a result, the effects of the invention, that is, the improvement of the characteristics of the multilayer structure, such as gas barrier properties and durability of the characteristics can be more effectively
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[0045] The lower limit of the thickness of the multilayer structure is preferably 0.1 pm, more preferably 1 pm, and even more preferably 5 pm. On the other hand, the upper limit of the thickness of the multilayer structure is preferably 1,000 μιτι, more preferably 700 pm, and even more preferably 500 pm. When the thickness of the multilayer structure is less than the lower limit described above, the force becomes insufficient, so the use of the multilayer structure can be difficult. On the contrary, when the thickness of the multilayer structure is beyond the upper limit described above, flexibility, conformability and the like deteriorate, thus an increase in production costs can be presented. Note that the thickness of the multilayer structure can be determined by measuring the thickness of the cross section at points selected arbitrarily from the multilayer structure.
[0046] The lower limit of the average thickness of layer A in terms of a single layer is preferably 0.01 pm, more preferably 0.05 pm, and even more preferably 0.1 pm. On the other hand, the upper limit of the average thickness of layer A in terms of a single layer is preferably 10 pm, more preferably 7 pm, even more preferably 5 pm, and particularly preferably 2 pm. When the average thickness of layer A in terms of a single layer is less than the lower limit described above, formation with a uniform thickness becomes difficult, so that the gas barrier properties and their durability of the multilayer structure can deteriorate. if. On the contrary, when the average thickness of layer A in terms of a single layer is beyond the upper limit described above, it becomes difficult to increase the number of layers, if the entire multilayer structure has a thickness
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15/158 identical mean, with which the effect of improving the gas barrier properties, due to the multilayer, as described above can be effected, and elasticity and thermoformability of the multilayer structure can be deteriorated. It should be noted that the average thickness of layer A in terms of a single layer refers to a value obtained by dividing the total thickness of all layers A included in the multilayer structure by the number of layers A.
[0047] For a similar reason, the lower limit of the average thickness of layer B, in terms of a single layer is preferably 0.01 pm, more preferably 0.05 pm, and even more preferably 0.1 pm . On the other hand, the upper limit of the average thickness of layer B, in terms of a single layer, is preferably 10 pm, more preferably 7 pm, even more preferably 5 pm, and especially preferably 2 pm. It should be noted that the average thickness of layer B, in terms of a single layer, also refers to a value obtained by dividing the total thickness of all layers B included in the multilayer structure by the number of layers B.
Layer A [0048] Layer A is made up of a resin composition containing a gas barrier resin. Since the resin composition that constitutes layer A contains a gas barrier resin, the multilayer structure, which is superior in gas barrier properties, can be obtained.
[0049] The gas barrier resin has a function of preventing gas permeabilization, specifically, it has an oxygen transmission rate, as determined according to a method described in JIS-K7126 (isopyethic method) under conditions including 20 ° C and 65% RH not exceeding 100 mL · 20 pm / (m ² · day · atm). It should be noted that the oxygen transmission rate of the
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16/158 gas barrier resin used in the present invention is preferably not more than 50 ml · 20 pm / (m ² · day · atm), and more preferably not more than 10 ml · 20 pm / (m ² · day · atm).
[0050] Such a gas barrier resin is exemplified by an ethylene-vinyl alcohol copolymer (hereinafter also referred to as EVOH.), A polyamide resin, a polyester resin, polyvinylidene chloride, an acrylonitrile copolymer. , polyvinylidene fluoride, polychlorinated trifluoroethylene, polyvinyl alcohol, and the like.
[0051] Of these resins having gas barrier properties, EVOH, polyamide resins and polyester resins are preferred in view of the gas barrier properties, and EVOH is particularly preferred in light of not only the gas barrier properties, but also fusion formability, layer B adhesiveness, and the like.
Polyamide Resin [0052] Polyamide resin is a polymer with an amide bond, and can be obtained by lactam ring opening polymerization, polycondensation of aminocarboxylic acid or diamine with dicarboxylic acid, or similar.
[0053] Examples of the lactam include ε-caprolactam, ω laurolactam, and the like.
[0054] Examples of aminocarboxylic acid include 6aminocaproic acid, 11-aminoundecanoic acid, 12aminododecanoic acid, paraminomethylbenzoic acid, and the like.
[0055] Examples of the diamine include tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine,
2,2,4-trimethylexa methylenediamine and 2,4,4-trimethylhexamethylenediamine,
5-methylnonamethylene diamine, m-xylylenediamine, p-xylylenediamine, 1,3bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1 amino-3-aminomethyl-3,5,5- trimethyl cyclohexane hexane, bis (4-aminocyclePetition 870190056670, of 6/19/2019, page 20/172
17/158 hexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis- (4 aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, and the like.
[0056] Dicarboxylic acid is exemplified by succinic acid, glutaric acid, adipic acid, pyelic acid, submeric acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, decalindicarboxylic acid, norbornanodicarboxylic acid, tricyclododicarboxylic acid, tricyclodecododicanic acid , 3,9-bi (2-carboxyethyl) 2,4,8,10-tetraoxaspiro [5.5] undecane, trimellitic acid, trimethic acid, pyromelitic acid, tricarbalyl acid, terephthalic acid, isophthalic acid, phthalic acid, 2 -methylterephthalic, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, tetraphphorodicarboxylic acid, and the like.
[0057] Exemplary method for polycondensation, which can be employed in the synthesis of polyamide resin, includes a method in which polycondensation is allowed in the molten state, and a method in which polycondensation is once allowed in a molten state to obtain low viscosity polyamide, followed by heat treatment in a solid phase state (solid phase polymerization, generally referred to). Exemplary method for polycondensation in the molten state that can be employed includes a method in which an aqueous solution of a nylon salt of diamine and dicarboxylic acid is heated under pressure, and then polycondensation is allowed in a molten state while eliminating water and condensed water, a method in which diamine is directly added to the dicarboxylic acid in a molten state, and then the polycondensation is left under normal pressure and the like.
[0058] Examples of specific polyamide resin that is a polycondensate of the compound or the like include aliphatic polyamide resins, such as polycaprolactam (nylon 6), polyilaurolactam (nylon
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12), polyhexamethylenediadipamide (nylon 66), polyhexamethyleneazelamide (nylon 69), polyhexamethylenessebacamide (nylon 610), nylon 46, nylon 6/66, nylon 6/12, and a condensation product of 11-aminane acid 11), aromatic polyamide resins, such as polyhexamethyleneisophthalamide (nylon 6IP), m-xylenediamine / adipic acid copolymer (nylon MXD6), and mxylenediamine / adipic acid / isophthalic acid copolymer, and the like. These can be used alone or as a mixture of two or more of them.
[0059] Among these polyamide resins, MXD6 nylon having superior gas barrier properties is preferred. With respect to an MXD6 nylon diamine component, mxylylene diamine is preferably included in an amount of not less than 70 mol%. Whereas, with respect to a dicarboxylic acid component, adipic acid is preferably included in an amount of not less than 70 mol%. When MXD6 nylon is obtained from the mixed monomer as described above, more superior gas barrier properties and mechanical performance can be achieved.
Polyester Resin [0060] Polyester resin is a polymer with an ester bond, and can be obtained by polycondensation of polyvalent carboxylic acid with polyol and the like. Examples of the polyester resin that can be used as a resin having gas barrier properties of the multilayer structure include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyglycolic acid (PGA), aromatic liquid crystal polyesters, and the like. These can be used alone or as a mixture of two or more of them. Among these polyester resins, PGA and aromatic liquid crystal polyesters are preferred due to the degree of proPetition 870190056670, of 06/19/2019, p. 22/172
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PGA [0061] PGA is a homopolymer or copolymer with a structural unit represented by -O-CH2-CO- (GA). The content of said structural unit (GA) in PGA is preferably not less than 60% by weight, more preferably not less than 70% by weight, and even more preferably not less than 80% by weight. Likewise, the upper limit of the content is preferably 100% by weight. When the content of the structural unit (GA) is below the lower limit described above, the gas barrier properties may not be sufficiently achieved.
[0062] Exemplary method for the production of PGA includes (1) a method of synthesis by means of dehydrating polycondensation of glycolic acid, (2) a method of synthesis by means of de-alcoholisation polycondensation of an alkyl ester of glycolic acid (3) one synthesis method by means of glycolide ring opening polymerization (1,4-dioxane-2,5-dione), and the like.
[0063] Exemplary method for synthesizing PGA as a copolymer may include the methods in which copolymerization is carried out in each synthesis method described above, using as a comonomer, for example, [0064] a cyclic monomer such as ethylene oxalate (1 , 4dioxane-2,3-dione), lactide, lactones (for example, β-propiolactone, β-butyrolactone, pivalolactone, γ-butyrolactone, δ-valerolactone, β-methylδ-valerolactone, ε-caprolactone, etc.), trimethylene carbonate or 1,3dioxane;
[0065] hydroxycarboxylic acid, such as lactic acid, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid or 6-hydroxycaproic acid, or an alkyl ester thereof;
[0066] a mixture of aliphatic diol such as ethylene glycol or 1,4 Petition 870190056670, from 19/06/2019, p. 23/172
20/158 butanediol with substantially equimolar aliphatic dicarboxylic acid such as succinic acid or adipic acid or an alkyl ester thereof; or similar, [0067] in appropriate combination with glycolide, glycolic acid or an alkyl ester of glycolic acid.
[0068] In a specific ring-opening polymerization method described above in section (3), glycolide is heated to a temperature of about 120 ° C to about 250 ° C in the presence of a small amount of a catalyst (eg example, a cationic catalyst such as organic tin carboxylate, tin halide or antimony halide). The ring-opening polymerization is preferably carried out by a block polymerization process or solution polymerization process.
[0069] In ring-opening polymerization, the glycolide used as a monomer can be obtained by a sublimation depolymerization process, solution phase depolymerization process, or the like, of a glycolic acid oligomer.
[0070] A typical solution phase depolymerization process includes, for example, (1) heating a mixture containing a glycolic acid oligomer and at least one high-boiling polar organic solvent having a boiling point within from 230 to 450 ° C, under normal pressure or reduced pressure at a temperature at which depolymerization of the oligomer occurs, (2) dissolving the oligomer in a solvent to a residual proportion (volume ratio) of the melting phase of the oligomer becomes no greater than 0.5, (3) allow the oligomer to be depolymerized by additional heating at the same temperature, (4) distillation of the cyclic dimer ester produced (glycolide), together with the high polar organic solvent boiling point, and (5) recovering the glycolide from the distillate.
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21/158 [0071] Examples of high boiling organic polar solvent include phthalic acid bis (alkoxyalkyl ester) such as di (2methoxyethyl) phthalate, alkylene glycol dibenzoate such as diethylene glycol dibenzoate, aromatic carboxylate esters such as phthalate benzylbutyl and dibutyl phthalate, aromatic phosphoric acid esters such as tricresylphosphate, and the like. In addition, together with the high boiling polar organic solvent, polypropylene glycol, polyethylene glycol, tetraethylene glycol or the like can be used in combination as an oligomer solubilizing agent, if necessary. Integral aromatic liquid crystal polyester [0072] Integral aromatic liquid crystal polyester is a liquid crystalline polyester in which the polyvalent carboxylic acid and polyol supplied as monomers are both an aromatic compound. Integral aromatic liquid crystal polyester can be obtained by polymerization according to a well-known method similar to general polyesters.
[0073] The polyvalent aromatic carboxylic acid is exemplified by terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3 ' -biphenyldicarboxylic acid, 4,4'methylene dibenzoic acid, diphenic acid and the like. These can be used alone or as a mixture of two or more of them.
[0074] The aromatic polyol is exemplified by hydroquinone, methylhydroquinone, 4,4'-dihydroxydiphenyl, phenylhydroquinone, resorcinol, 3,4'bisphenol A, and the like. These can be used alone or as a mixture of two or more of these.
[0075] Furthermore, the integral aromatic liquid crystalline polyester can also be obtained by polymerizing an aromatic compound that has a hydroxy group and a carboxyl group such as
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22/158 hydroxybenzoic acid or hydroxinaftoic acid, etc., or copolymerizing the polyvalent aromatic carboxylic acid and aromatic polyol. EVOH [0076] Hereinafter, EVOH appropriately used as a gas barrier resin of the multilayer structure of the present invention is explained in detail.
[0077] EVOH included in the layer A resin composition features an ethylene unit and a vinyl alcohol unit as main structural units. It is to be noted that EVOH may include one type or a plurality of types of other structural units in addition to the ethylene unit and the vinyl alcohol unit.
[0078] EVOH is normally obtained by polymerizing ethylene with vinyl ester, and saponification of the resulting ethylene vinyl ester copolymer.
[0079] The lower limit of the content of ethylene units in EVOH (i.e., the ratio of the number of ethylene units to the total number of monomeric units in EVOH) is preferably 3 mol%, more preferably 10% in mol, even more preferably 20 mol%, and particularly preferably 25 mol%. On the other hand, the upper limit of the content of ethylene units in EVOH is preferably 70 mol%, more preferably 60 mol%, even more preferably 55 mol%, and particularly preferably 50 mol%. When the content of ethylene units in EVOH is below the lower limit described above, water resistance, resistance to hot water gas barrier properties, under highly humid conditions of the multilayer structure can be deteriorated, or the melt formability of the multilayer structure can be harmed. On the contrary, when the content of ethylene units in EVOH is beyond the upper limit described above, the gas barrier properties of the multilayer structure can be deteriorated.
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23/158 [0080] The lower limit of the degree of saponification of EVOH (ie the ratio of the number of units of vinyl alcohol to the total number of units of vinyl alcohol and units of vinyl ester in EVOH) is, preferably 80 mol%, more preferably 95 mol%, and particularly preferably 99 mol%. On the other hand, the upper limit of the degree of saponification of EVOH is preferably 99.99 mol%. When the degree of saponification of EVOH is below the lower limit described above, melt formability may be impaired, and, in addition, the gas barrier properties of the multilayer structure may be deteriorated, or the dye resistance and / or moisture resistance can be unsatisfactory. On the contrary, when the degree of saponification of EVOH is beyond the upper limit described above, the improvement of gas barrier and similar properties, with respect to an increase in EVOH production costs can be expected to an unsatisfactory extent. Such EVOH can be used alone, however, a modality in which such EVOH is used as a mixture with EVOH having a degree of saponification greater than 99 mol% is also suitable.
[0081] It is preferred that the G content (mol%) of the 1,2-glycol structural linkers in EVOH meets the following Formula (2), and the intrinsic viscosity is not less than 0.05 L / g , and not more than 0.2 L / g. In the following Formula (2), E represents the content of ethylene units (mol%) in EVOH (where, E <64 (mol%)).
G <1.58-0.0244 x E (2) [0082] When the resin composition of layer A includes EVOH having such a G content of 1,2-glycol bonding structural units and an intrinsic viscosity, a decreasing characteristic the moisture dependence of the gas barrier properties of the resulting multilayer structure can be displayed, and favorable transparency
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24/158 and gloss are provided, while lamination with another thermoplastic resin can be facilitated. In this way, the applicability of the multilayer structure as a material for packaging food and the like can be improved. It should be noted that the G content of the 1,2-glycol binding structural units can be determined according to the method described by S. Aniya et al., (Analytical Science Vol. 1, 91 (1985)), by by means of a nuclear magnetic resonance process, at a temperature of 90 ° C with a solution of dimethyl sulfoxide as a sample of EVOH.
[0083] EVOH preferably has at least one selected from the group consisting of structural units (I) and (II). The lower limit of the content of at least one selected from the structural units (I) or (II) with respect to the entire structural units is preferably 0.5 mol%, more preferably 1 mol%, and even more preferably 1 , 5 mol%. On the other hand, the upper limit of the content of at least one selected from the structural units (I) or (II) is preferably 30% by mol, more preferably 15% by mol, and even more preferably 10% by mol. When the layer A resin composition has the structural unit represented by Formula (s) (I) and / or (II) above at a proportion falling within the above range, flexibility and processing characteristics of the layer composition resin A are improved, and therefore allows the elasticity and thermoformability of the multilayer structure to be improved.
[0084] In structural units (I) and (II), the aliphatic hydrocarbon group having 1 to 10 carbon atoms is exemplified by an alkyl group, an alkenyl group and the like, the alicyclic hydrocarbon group having 3 to 10 carbon atoms is exemplified by a cycloalkyl group, a cycloalkenyl group and the like, and the aromatic hydrocarbon group having 6 to 10 carbon atoms is
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25/158 exemplified by a phenyl group, and the like.
[0085] In structural unit (I), it is preferred that R ¹ , R ² and R ³ each independently represent a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, a hydroxymethyl group or a hydroxyethyl group. Among these, it is more preferred that each of them independently represents a hydrogen atom, a methyl group, a hydroxyl group or a hydroxymethyl group. When R ¹ , R ² and R ³ each represent these options, the elasticity and thermoformability of the multilayer structure can be further improved.
[0086] Although the method for allowing EVOH to include the structural unit (I) is not particularly limited, for example, a method in which a monomer derived to the structural unit (I) is copolymerized in the polymerization of ethylene and vinyl ester can be involved. The monomer derived for the structural unit (I) is exemplified by alkene, such as propylene, butylene, pentene and hexene; alkene having a hydroxyl group and / or an ester group such as 3-hydroxy-1-propene, 3-acyloxy-1-propene, 3-acyloxy-1-butene, 4acyloxy-1-butene, 3,4-diacyloxy-1 -butene, 3-acyloxy-4-hydroxy-1-butene, 4acyloxy-3-hydroxy-1-butene, 3-acyloxy-4-methyl-1-butene, 4-acyloxy-2-methyl1-butene, 4-acyloxy -3-methyl-1-butene, 3,4-diacyloxy-2-methyl-1-butene, 4-hydroxy-1-pentene, 5-hydroxy-1-pentene, 4,5-dihydroxy-1-pentene, 4acyloxy-1 -pentene, 5-acyloxy-1-pentene, 4,5-diacyloxy-1-pentene, 4-hydroxy-3-methyl-1-pentene, 5-hydroxy-3-methyl-1-pentene, 4,5-dihydroxy -3methyl-1-pentene, 5,6-dihydroxy-1-hexene, 4-hydroxy-1-hexene, 5-hydroxy1-hexene, 6-hydroxy-1-hexene, 4-acyloxy-1-hexene, 5 -acyloxy-1-hexene,
6-acyloxy-1-hexene and 5,6-diacyloxy-1-hexene. Of these, depending on the reactivity for copolymerization, and the gas barrier properties of the resulting multilayer structure, propylene, 3-acyloxy-1-propene, 3acyloxy-1-butene, 4-acyloxy-1-butene, and 3.4 - diacetoxy-1-butene are preferred. Specifically, among these, propylene, 3-acetoxy-1
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26/158 propene, 3-acetoxy-1-butene, 4-acetoxy-1-butene, and 3,4-diacetoxy-1-butene are preferred, and of these, 3,4-diacetoxy-1-butene is particularly preferred. In the case of the alkene with an ester, it is derived to the structural unit (I) during the saponification reaction. [0087] In the structural unit (II) above, it is preferred that R ⁴ and R ⁵ both represent a hydrogen atom. In particular, it is more preferred that R ⁴ and R ⁵ both represent a hydrogen atom, one of R ⁶ and R ⁷ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the remainder represents a hydrogen atom. The aliphatic hydrocarbon group is preferably an alkyl group or an alkenyl group. In light of the particular note taken for the gas barrier properties of the multilayer structure, it is particularly preferred that one of R ⁶ and R ⁷ represents a methyl group or an ethyl group, and the rest represents a hydrogen atom. Alternatively, it is also particularly preferred that one of R ⁶ and R ⁷ represents a substituent represented by (CH2) hOH (where, h is an integer from 1 to 8), and the rest represents a hydrogen atom. In the substituent represented by (CH2) hOH, h is preferably an integer from 1 to 4, more preferably 1 or 2, and particularly preferable 1.
[0088] Although the method for allowing EVOH to include structural unit (II) is not particularly limited, for example, a method in which EVOH obtained by a saponification reaction is allowed to react with a monovalent epoxy compound to allow EVOH to include the structural unit (II) can be employed. As the monovalent epoxy compound, a compound represented by any of the following Formulas (III) to (IX) is suitably used.
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27/158
[0089] In Formulas (III) to (IX) above, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, as an alkyl group or an alkenyl group, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, such as a cycloalkyl group or a cycloalkenyl group, or a hydrocarbon group
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28/158 aliphatic grandson having 6 to 10 carbon atoms such as a phenyl group; ei, j, k, p, eq represent an integer from 1 to 8. [0090] Examples of the monovalent epoxy compound represented by Formula (III) above include epoxyethane (ethylene oxide), epoxypropane, 1,2-epoxybutane, 2 , 3-epoxybutane, 3-methyl-1,2-epoxybutane,
1,2-epoxipentane, 2,3-epoxipentane, 3-methyl-1,2-epoxipentane, 4-methyl-
1.2- epoxipentane, 4-methyl-2,3-epoxipentane, 3-ethyl-1,2-epoxipentane,
1.2- epoxyhexane, 2,3-epoxyhexane, 3,4-epoxyhexane, 3-methyl-1,2-epoxyhexane, 4-methyl-1,2-epoxyhexane, 5-methyl-1,2-epoxyhexane, 3-ethyl-
1,2-epoxyhexane, 3-propyl-1,2-epoxyhexane, 4-ethyl-1,2-epoxyhexane, 5methyl-1,2-epoxyhexane, 4-methyl-2,3-epoxyhexane, 4-ethyl-2, 3-epoxyhexane, 2-methyl-3,4-epoxyhexane, 2,5-dimethyl-3,4-epoxyhexane, 3methyl-1,2-epoxyheptane, 4-methyl-1,2,2-epoxyheptane, 5-methyl-1, 2epoxyheptane, 6-methyl-1,2-epoxyheptane, 3-ethyl-1,2-epoxyheptane, 3propyl-1,2-epoxyheptane, 3-butyl-1,2-epoxyheptane, 4-ethyl-1,2epoxyheptane, 4- propyl-1,2-epoxyheptane, 5-ethyl-1,2-epoxyheptane, 4methyl-2,3-epoxyheptane, 4-ethyl-2,3-epoxyheptane, 4-propyl-2,3epoxyheptane, 2-methyl-3, 4-epoxyheptane, 5-methyl-3,4-epoxyheptane, 5ethyl-3,4-epoxyheptane, 2,5-dimethyl-3,4-epoxyheptane, 2-methyl-5-ethyl-3,4epoxyheptane, 1, 2- epoxyheptane, 2,3-epoxyheptane, 3,4-epoxyheptane, 1,2-epoxyoctane, 2,3-epoxyoctane, 3,4-epoxyoctane, 4,5-epoxyoctane,
1,2-epoxinonane, 2,3-epoxinonane, 3,4-epoxinonane, 4,5-epoxinonane, 1,2-epoxidecane, 2,3-epoxidecane, 3,4-epoxidecane,
4,5-epoxidecane, 5,6-epoxidecane, 1,2-epoxyundecane, 2,3-epoxyundecane, 3,4-epoxyundecane, 4,5-epoxyundecane, 5,6epoxyundecane, 1,2-epoxidedecane, 2,3- epoxidedecan, 3,4epoxidedecan, 4,5-epoxidedecan, 5,6-epoxidedecan, 6,7epoxidedecan, epoxyethylbenzene, 1-phenyl-1,2-propane, 3-phenyl-1,2epoxypropane, 1-phenyl-1,2- epoxybutane, 3-phenyl-1,2-epoxipentane, 4-phenyl-1,2-epoxipentane, 5-phenyl-1,2-epoxipentane, 1-phenyl-1,2Petition 870190056670, 06/19/2019, p. 32/172
29/158 epoxyhexane, 3-phenyl-1,2-epoxyhexane, 4-phenyl-1,2-epoxyhexane, 5-phenyl-
1.2- epoxyhexane, 6-phenyl-1,2-epoxyhexane, and the like.
[0091] Examples of the monovalent epoxy compound represented by Formula (IV) above include methylglycidyl ether, ethylglycidyl ether, isopropyl glycidyl ether, n-butylglycidyl ether, glycidyl isobutyl ether, tert-butylglycidyl ether, 1,2-ether 3-pentyloxypropane, 1,2-epoxy-3hexyloxypropane, 1,2-epoxy-3-heptyloxypropane, 1,2-epoxy-4-phenoxybutane, 1,2-epoxy-4-benzyloxybutane, 1,2-epoxy-5-methoxypentane,
1.2- epoxy-5-ethoxypentane, 1,2-epoxy-5-propoxypentane, 1,2-epoxy-5-butoxypentane, 1,2-epoxy-5-pentyloxypentane, 1,2-epoxy-5hexyloxypentane, 1,2- epoxy-5-phenoxypentane, 1,2-epoxy-6-methoxyhexane,
1.2- epoxy-6-ethoxyhexane, 1,2-epoxy-6-propoxyhexane, 1,2-epoxy-6butoxyhexane, 1,2-epoxy-6-heptyloxyhexane, 1,2-epoxy-7-methoxyheptane,
1.2- epoxy-7-ethoxyheptane, 1,2-epoxy-7-propoxyheptane, 1,2-epoxy-7butoxyheptane, 1,2-epoxy-8-methoxyoctane, 1,2-epoxy-8-ethoxyoctane, 1,2-epoxy- 8-butoxioctane, glycidol, 3,4-epoxy-1-butanol, 4,5-epoxy-1pentanol, 5,6-epoxy-1-hexanol, 6,7-epoxy-1-heptanol, 7,8-epoxy- 1octanol, 8,9-epoxy-1-nonanol, 9,10-epoxy-1-decanol, 10,11-epoxy-1undecanol, and the like.
[0092] Examples of the monovalent epoxy compound represented by Formula (V) above include monoglycidyl ethyl ether glycol, monoglycidyl propanediol ether, monoglycidyl butanediol ether, pentanediol monoglycidyl ether, hexanediol monoglycidyl ether, monoglycidyl ether and monoglycidyl ether octanodiol, and the like.
[0093] Examples of the monovalent epoxy compound represented by Formula (VI) above include 3- (2,3-epoxy) -propoxy-1-propene, 4 (2,3-epoxy) -propoxy-1-butene, 5- ( 2,3-epoxy) -propoxy-1-pentene, 6- (2,3-epoxy) -propoxy-1-hexene, 7- (2,3-epoxy) -propoxy-1-heptene, 8- (2,3-epoxy) propoxy-1-octene, and the like.
[0094] Examples of the represented monovalent epoxy compound
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30/158 by Formula (VII) above include 3,4-epoxy-2-butanol, 2,3-epoxy-1-butanol, 3,4-epoxy-2-pentanol, 2,3-epoxy-1-pentanol, 1, 2-epoxy-3pentanol, 2,3-epoxy-4-methyl-1-pentanol, 2,3-epoxy-4,4-dimethyl-1-pentanol
2,3-epoxy-1-hexanol, 3,4-epoxy-2-hexanol, 4,5-epoxy-3-hexanol, 1,2-epoxy-3-hexanol, 2,3-epoxy-4-methyl-1- hexanol, 2,3-epoxy-4-ethyl-1-
hexanol, 2,3-epoxy-4,4-dimethyl-1-hexanol, 2,3-epoxy-4,4-diethyl-1- hexanol, 2,3-epoxy-4-methyl-4-ethyl-1-hexanol, 3,4-epoxy-5-methyl-2- hexanol, 3,4-epoxy-5,5-dimethyl-2-hexanol, 3,4-epoxy-2-eptanol, 2,3-
epoxy-1-eptanol, 4,5-epoxy-3-eptanol, 2,3-epoxy-4-eptanol, 1,2-epoxy-3eptanol, 2,3-epoxy-1-octanol, 3,4-epoxy 2-octanol, 4,5-epoxy-3-octanol,
5,6-epoxy-4-octanol, 2,3-epoxy-4-octanol, 1,2-epoxy-3-octanol, 2,3-epoxy-1-nonanol, 3,4-epoxy-2-nonanol, 4, 5-epoxy-3-nonanol, 5,6-epoxy-
4-nonanol, 3,4-epoxy-5-nonanol, 2,3-epoxy-4-nonanol, 1,2-epoxy-3-
nonanol, 2,3-epoxy-1-decanol, 3,4-epoxy-2-decanol, 4,5-epoxy-3- decanol, 5,6-epoxy-4-decanol, 6,7-epoxy-5-decanol, 3,4-epoxy-5-
decanol, 2,3-epoxy-4-decanol, 1,2-epoxy-3-decanol, and the like.
[0095] Examples of the monovalent epoxy compound shown
by Formula (VIII) above include 1,2-epoxycyclopentane, 1,2epoxycyclohexane, 1,2-epoxycycloheptane, 1,2 epoxycyclooctane-, 1,2-epoxycyclononane, 1,2-epoxycyclodecane, 1, 2 -epoxycyclodecane,, 2-epoxycyclododecane, and the like.
[0096] Examples of the monovalent epoxy compound represented by the above formula (IX) include 3,4-epoxycyclopentene, 3,4-epoxycyclohexene, 3,4-epoxycycloheeptene, 3,4-epoxycyclooctene, 3,4epoxycyclononene, 1,2 -epoxycyclodecene, 1,2-epoxycyclodecene, 1,2epoxycyclododecene, and the like.
[0097] Among the aforementioned monovalent epoxy compounds, epoxy compounds having 2 to 8 carbon atoms are preferred. Particularly, in light of the easy manipulation of the compound, and reactivity with EVOH, the monovalent epoxy compound is shown on 8/20/190056670, from 06/19/2019, p. 34/172
31/158 places carbon atoms of more preferably 2 to 6, and even more preferably 2 to 4. In addition, among the monovalent epoxy compounds represented by the above formula, the compounds represented by Formula (III) or (IV) are particularly preferred. Specifically, due to the reactivity with EVOH and gas barrier properties of the resulting multilayer structure, 1,2-epoxybutane,
2,3-epoxybutane, epoxypropane, epoxyethane and glycidol are preferred, and of these, epoxypropane and glycidol are particularly preferred. In applications for which aspects of good hygiene are required, such as food packaging applications, beverage packaging applications and medical drug packaging applications, 1,2 epoxybutane, 2,3-epoxybutane, epoxypropane, or epoxyethane are preferably used as the epoxy compound, and epoxypropane are particularly preferably used.
[0098] Next, a method for the production of EVOH is explained in detail. A method for copolymerizing ethylene and a vinyl ester is not particularly limited and, for example, any of solution polymerization, suspension polymerization, emulsion polymerization, mass polymerization can be employed. In addition, any continuous or batch type system can be adopted.
[0099] The vinyl ester that can be used for polymerization is a fatty acid vinyl ester, such as vinyl acetate, vinyl propionate, vinyl pivalate.
[00100] In polymerization, in addition to the components mentioned above, a copolymerizable monomer, for example, different from those previously described, an alkene; unsaturated acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or itaconic acid, or an anhydride, salt, or mono- or dialkyl ester thereof; nitrile such as acrylonitrile or methacrylonitrile; amide, such as acrylamide
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32/158 da or methacrylamide; olefin sulfonic acid such as vinyl sulfonic acid, allyl sulfonic acid or metalyl sulfonic acid, or a salt thereof, alkyl vinyl ethers, vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride and the like can be copolymerized as a copolymerization component in a small amount. In addition, as a copolymerization component, a vinylsilane compound can be included in an amount of not less than 0.0002 mol% and not more than 0.2 mol%. Examples of the vinylsilane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (B-methoxyethoxy) silane, γ-methacryloloxypropyl methoxysilane, and the like. Of these, vinyltrimethoxysilane or vinyltriethoxysilane can be used appropriately.
[00101] The solvent that can be used for polymerization is not particularly limited, as it is an organic solvent that can dissolve ethylene, vinyl ester and ethylene-vinyl ester copolymer. As such a solvent, for example, alcohol, such as methanol, ethanol, propanol, n-butanol or tert-butanol; dimethyl sulfoxide, or similar, can be used. Of these, methanol is particularly preferred in terms of ease of separation and removal after the reaction. [00102] As the catalyst for use in polymerization, for example, an azonitrile based initiator such as 2,2azobisisobutyronitrile, 2,2-azobis- (2,4-dimethylvaleronitrile), 2,2-azobis (4-methoxy- 2,4-dimethylvaleronitrile) or 2,2-azobis- (2-cyclopropylpropionitrile); an organic peroxide based initiator such as isobutyryl peroxide, cumil peroxyneodecanoate, diisopropyl peroxycarbonate, di-n-propylperoxydicarbonate, t-butylperoxyneodecanoate, laurolperoxide, benzolperoxide or t-butylhydroperoxide, or the like can be used.
[00103] The polymerization temperature is 20 to 90 ° C, and preferably 40 to 70 ° C. The polymerization time is 2 to 15 hours, and from
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33/158 preferably 3 to 11 hours. The degree of polymerization is 10 to 90%, and preferably 30% to 80, with respect to the charged vinyl ester. The resin content in the solution after polymerization is 5 to 85%, and preferably 20% to 70.
[00104] After polymerization, for a predetermined period of time or after reaching a predetermined degree of polymerization, a polymerization inhibitor is added as needed, and the unreacted ethylene gas is eliminated by evaporation, followed by removal of unreacted vinyl ester. In an exemplary method that can be employed for removing unreacted vinyl ester, for example, the copolymer solution is continuously supplied at a constant speed from a tower packed up with Raschig rings, while the vapor from a organic solvent such as methanol is blown to the bottom of the tower, a mixed vapor stream of organic solvent such as methanol and the unreacted vinyl ester is removed by distillation from the top of the tower, while the copolymer solution from which the unreacted vinyl ester has been removed is recovered from the bottom of the tower.
[00105] Then, an alkaline catalyst is added to the copolymer solution, and the copolymer is saponified. The saponification method can be performed by any system in a continuous or discontinuous process. Examples of the alkaline catalyst include sodium hydroxide, potassium hydroxide, alkali metal alcoholate and the like.
[00106] Saponification conditions involve, for example, in the case of a batch system, the concentration of the copolymer solution from 10 to 50%, the reaction temperature from 30 to 65 ° C, the amount of catalyst used from 0.02 to 1.0 mol per mol of vinyl ester structural unit, and the saponification time of 1 to 6 hours.
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34/158 [00107] Since EVOH after the saponification reaction contains the alkaline catalyst, salt by-products, such as sodium acetate and potassium acetate, and other impurities, are preferably eliminated, if necessary by neutralization and washing. In this process, when EVOH after the saponification reaction is washed with water, such as ion exchange water, which is practically free of metal ions, chloride ions and the like, a part of sodium acetate, potassium acetate and the like can stay.
[00108] The resin composition that constitutes layer A may contain one or a plurality of types of compounds selected from a phosphate compound, a carboxylic acid and a boron compound, depending on the embodiment of the invention. When such a phosphate compound, a carboxylic acid or a boron compound is contained in the layer A resin composition, various types of multilayer structure performance can be improved.
[00109] Specifically, when a phosphate compound is contained in the layer A resin composition containing EVOH and the like, the thermal stability of the multilayer structure during melt formation can be improved. The phosphate compound is not particularly limited, and is exemplified by various types of acids such as phosphoric acid and phosphorous acid, and salts thereof, and the like. Phosphate can be included in any form, such as, for example, primary phosphate, secondary phosphate or tertiary phosphate, and their counter-cationic species are not particularly limited, which is preferably an alkali metal ion or an alkaline earth metal ion. In particular, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate or potassium hydrogen phosphate is preferred in light of the excellent effects of improving thermal stability.
[00110] The lower limit of the content of the phosphate compound (the content of
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35/158 phosphate compound in terms of the phosphoric acid group equivalent in the dry resin composition of layer A) is preferably 1 ppm, more preferably 10 ppm, and even more preferably 30 ppm. On the other hand, the upper limit of the content of the phosphate compound is preferably 10,000 ppm, more preferably 1,000 ppm, and even more preferably 300 ppm. When the content of the phosphate compound is below the lower limit described above, the color during melting tends to be significant. Since this trend is notable when the heat history is repeated in particular, a product obtained by the formation of a sediment from the resin composition may lack probability of recovery. On the contrary, when the content of the phosphate compound is beyond the upper limit described above, the product formed can easily generate gels and descendants.
[00111] In addition, the carboxylic acid included in the layer A resin composition containing EVOH and the like is effective in controlling the pH of the resin composition, and preventing gelation to improve thermal stability. Carboxylic acid is preferably acetic acid or lactic acid depending on costs and the like.
[00112] The lower limit of the carboxylic acid content (the carboxylic acid content in the layer A dry resin composition) is preferably 1 ppm, more preferably 10 ppm, and even more preferably 50 ppm. On the other hand, the upper limit of the carboxylic acid content is preferably 10,000 ppm, more preferably 1,000 ppm, and even more preferably 500 ppm. When the content of the carboxylic acid is below the lower limit described above, staining may occur during melting. On the contrary, the carboxylic acid content is beyond the upper limit described above, the interlayer stickiness may be insufficient.
[00113] In addition, the boron compound included in the composition of
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36/158 layer A resin, containing EVOH or similar, is effective in improving thermal stability. In detail, when the boron compound is added to the resin composition made up of EVOH, it is believed that a chelate compound is produced between EVOH and the boron compound. In this way, the use of such an EVOH allows more superior thermal stability to be achieved than ordinary EVOH, and the mechanical properties can be improved. The boron compound is not particularly limited, and examples include boric acids, boric acid esters, boric acid salts, boron hydrides, and the like. Specifically, boric acids are exemplified by ortho-boric acid (H3BO3), meta-boric acid, tetraboric acid and the like; boric acid esters are exemplified by triethyl borate, trimethylborate and the like; boric acid salts are exemplified by alkali metal salts, alkaline earth metal salts and borax of the various types of boric acids described above and the like. Of these, ortho-boric acid is preferred.
[00114] The lower limit of the boron compound content (the boron compound content equivalent to that of boron in the layer A dry resin composition) is preferably 1 ppm, more preferably 10 ppm, and even more preferably 50 ppm. On the other hand, the upper limit of the boron compound content is preferably 2,000 ppm, more preferably 1,000 ppm, and even more preferably 500 ppm. When the content of the boron compound is below the lower limit described above, the effect of improving thermal stability by adding the boron compound may not be obtained. On the contrary, when the boron compound content is beyond the upper limit described above, gelation is likely to occur, and formation defects can be caused.
[00115] A process for including the phosphate compound, carboxylic acid or boron compound in the resin composition containing
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EVOH is not particularly limited, and, for example, a process in which the phosphate compound is added to the resin composition when a pellet or similar of the resin composition containing EVOH is prepared, followed by kneading can be suitably used. A process for adding to the resin composition is also not particularly limited, and illustrative examples include an addition process in the form of a dry powder, an addition process in a paste form, impregnated with a solvent, an addition process in a form suspended in a liquid, an addition process such as a solution dissolved in a solvent and the like. Of these, in the light of allowing homogeneous dispersion, an addition process such as a solution dissolved in a solvent is preferred. The solvent used in these methods is not particularly limited, and water is used appropriately due to the solubility of additives, advantages in terms of costs, ease of handling, safe operating environments, and the like. When so added, a metal salt, a resin other than EVOH and other additives and the like described later can be added concurrently. [00116] Furthermore, as a process to include the phosphate compound, carboxylic acid, boron compound, a process of immersing a tablet or tape obtained with an extruder or similar, after the saponification mentioned above in a solution containing these dissolved substances are also preferred in order to allow homogeneous dispersion. Also in this process, water is suitably used as a solvent, for reasons similar to those described above. By dissolving a metal salt described later for this solution, the metal salt and the phosphate compound and the like can be contained together.
[00117] The layer A resin composition preferably contains a compound that has a double bond conjugated to
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38/158 a molecular weight not exceeding 1,000. Due to including such a compound, the shade of the layer A resin composition is improved, therefore, a more favorable looking multilayer structure can be produced. Examples of such a compound include diene compounds conjugated to a structure in which at least two carbon-carbon double bonds and a carbon-carbon single bond are alternately linked, triene compounds having a structure in which three carbon-carbon double bonds and two single bonds carbon-carbon are alternately linked, the polyene compounds conjugated to a structure in which more carbon-carbon double bonds and carbon-carbon single bonds are alternately linked, the conjugated triene compounds, such as 2,4,6 octatriene, and the like. In addition, in the compound that has a conjugated double bond, a plurality of conjugated double bonds can be present independently in a molecule, and, for example, a compound, in which three conjugated trienes are included in the same molecule, such as oil of wood, may also be involved.
[00118] Examples of the compound having a conjugated double bond may have, for example, any of several other types of functional groups, such as a carboxyl group and salts thereof, a hydroxyl group, an ester group, a carbonyl group, an ether group, an amino group, an imino group, an amide group, a cyano group, a diazo group, a nitro group, a sulfone group, a sulfoxide group, a sulfite group, a thiol group, a sulfonic acid group and salts thereof, a group of phosphoric acid and salts thereof, a phenyl group, a halogen atom, a double bond, a triple bond, and the like. Such a functional group can be directly attached to a carbon atom in the conjugated double bond, or it can be attached to a position distant from the conjugated double bond. A league
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39/158 multiple tion in the functional group may be present in a position capable of conjugating with the conjugated double bond, and, for example, 1-phenylbutadiene having a phenyl group, and sorbic acid having a carboxyl group and the like, are also included in the compound that shows a conjugated double bond, as mentioned here. Specific examples of the compound include 2,4-diphenyl-4-methyl-1-pentene, 1,3-diphenyl-1-butene, 2,3-dimethyl-1,3-butadiene, 4-methyl-1,3-pentadiene, 1-phenyl -1, 3-butadiene, sorbic acid, myrcene, and the like. [00119] The conjugated double bond in the compound that has a conjugated double bond includes not only a conjugated double bond between aliphatic moieties such as 2,3-dimethyl-1,3-butadiene or sorbic acid, but also a conjugated double bond between the aliphatic and aromatic moieties, such as 2,4-diphenyl-4-methyl-1-pentene or 1,3-diphenyl-1-butene. Note that, in light of the possibility to obtain a multilayer structure showing a more superior appearance, the compound that includes a conjugated double bond between the aliphatic moieties is preferred, and a compound that includes a conjugated double bond having a polar group such as a carboxyl group. or a salt thereof, or a hydroxyl group is also preferred. In addition, a compound that includes a conjugated double bond between the aliphatic moieties and which have a polar group is particularly preferred.
[00120] The molecular weight of the compound having a conjugated double bond is preferably not more than 1,000. When the molecular weight is greater than 1,000, the smoothness of the surface, the extrusion stability and the like of the multilayer structure can be deteriorated. The lower limit of the content of the compound having a conjugated double bond having a molecular weight of not more than 1000 is, in light of the achievable effects, preferably 0.1 ppm, more preferably 1 ppm, even more preferably 3 ppm, and especially preferably 5 ppm. On the other hand, the upper limit of
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40/158 content of the compound is, in light of the achievable effects, preferably 3,000 ppm, more preferably 2,000 ppm, even more preferably 1,500 ppm, and particularly preferably 1,000 ppm.
[00121] A preferable process of adding the compound having a conjugated double bond may include, in the case of EVOH, for example, polymerizing, as described above, followed by adding the compound before the saponification described above, taking into account the improvement surface smoothness and extrusion stability. Although the reason is not necessarily clarified, it is believed that the compound that has a conjugated double bond serves to prevent deterioration of EVOH before saponification and / or during the saponification reaction.
[00122] The layer A resin composition may contain, in addition to the aforementioned additives, a resin other than gas barrier resin, or various additives such as a heat stabilizer, an ultraviolet-absorbing agent, a antioxidant, a dye and a filler in the range, so as not to harm the object of the present invention. When the layer A resin composition contains such additives, which are not the additives described above, the amount is preferably not more than 50% by weight, more preferably not more than 30% by weight, and particularly preferably not more than 10% by mass with respect to the total amount of the resin composition.
[00123] It is preferred that the layer A resin composition has a melting viscosity (η ^) as determined at a temperature of 210 ° C and a shear rate of 10 / s being not less than 1 x 10 ² Pa · if not more than 1 x 10 ⁴ Pa · if a melting viscosity (Q2a) as determined at a temperature of 210 ° C and a shear rate of 1,000 / s being not less than 1 x 10 ¹ Pa • if not more than 1 x 10 ³ Pa • s, and a proportion (n2A / n1A) of viscoPetição 870190056670, of 06/19/2019, p. 44/172
41/158 fusion strength meets the following Formula (1A):
-0.8 <(1/2) log10 (q2A / r | 1A) <-0.1 (1A).
[00124] It should be noted that appropriate ranges according to the melting viscosities (η ^) and (Q2a) and the melting viscosity ratio (η2Α / η1Α) can be applied particularly when the gas barrier resin contained in layer A resin composition is EVOH, or when layer A resin composition has a Vicat softening temperature of less than 180 ° C.
[00125] When the melt viscosity (η1Α) is less than 1 x 10 ² Pa • s, narrowing and agitation of the film can be significant in the formation of extrusion films, such as lamination with melt coextrusion or melt extrusion, increasing thus varying the thickness and reducing the width of the obtained multilayer structure and layer A before lamination, and thus it may be impossible to obtain a multilayer structure that is uniform and has a desired size. On the contrary, when the melt viscosity (η1Α) is beyond 1 x 10 ⁴ Pa • s, cleavage of the film becomes likely to occur and high-speed film formability is noticeably deteriorated particularly in the case where coextrusion lamination melting or forming with fusion extrusion is carried out under conditions with high speed regulation exceeding 100 m / min, and swelling of the mold is likely to occur, whereby obtaining a thin multilayer structure or layer A before lamination can be difficult.
[00126] Furthermore, when the melt viscosity (η2Α) is less than x 10 ¹ Pa • s, narrowing and shaking of the film in the formation of the extrusion film, such as lamination with melt coextrusion or melt extrusion can be significant, thereby intensifying the variation in thickness and reducing the width of the multilayer structure Petition 870190056670, of 6/19/2019, p. 45/172
42/158 of those obtained and of layer A before lamination. Conversely, when the melt viscosity (Q2a) is beyond 1 x 10 ³ Pa · s, a torque applied to the extruder becomes too high, and thus correcting the extrusion and welding line can probably be generated.
[00127] When a (1/2) logw (r | 2A / r | 1A) value calculated from the melting viscosity ratio (r | 2A / r | 1A) is less than -0.8, the cleavage of Film is likely to occur in extrusion film formation, such as fusion coextrusion lamination or fusion extrusion, whereby high speed film formability can be deteriorated. On the other hand, when the (1/2) logw (r2A / r1A) value is beyond 0.1, film narrowing and agitation occur in the formation of extrusion films, such as laminating with fusion coextrusion or fusion extrusion, in this way the variation in thickness and reduction in width can occur in the multilayer structure obtained and in layer A prior to the lamination. In this regard, the value of (1/2) logw (r2A / r1A) is more preferably not less than -0.6, and even more preferably not more than -0.2. It should be noted that the value (1/2) logw (r2A / r1A) in the above formula is determined from a graph of natural double logarithm of the melt viscosity along the ordinates in relation to the shear rate along the abscissa, as a slope of a line drawn through the connection of two points of the melting viscosity (r1A) and the melting viscosity (r2A). In addition, the melt viscosity (r1A) and melt viscosity (r2A) values as referred to herein are determined by a method described in the Examples below.
[00128] Furthermore, at a temperature higher than the Vicat softening temperature of the layer A or layer B resin composition, preferably layer A by 30 ° C, it is preferred that a melt viscosity (r1A) of the layer A resin composition as determined at a shear rate of 10 / s is not less than 1 x 10 ² Pa · s and not more than 1 x 10 ⁴ Pa · s, and a vis
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43/158 melt cosity (Π2α ') of the same as determined at a shear rate of 1,000 / sec is not less than 1 x 10 ¹ Pa · if not greater than 1 x 10 ³ Pa · s, and that the ratio ( Π2α '/ Π1α') of the melting viscosity meets the following Formula (1A '):
-0.8 <(1/2) log10 (Π2α '/ Π1α') <-0.1 (1A).
[00129] It should be noted that the appropriate range of the melting viscosities (Π1α ') and (Π2α'), and the ratio (Π2α '/ Π1α') of the melting viscosity can be particularly preferably applied in a case where the gas barrier resin included in the layer A resin composition is a resin other than EVOH, and a Vicat softening temperature of the layer A or layer B resin composition is not less than 180 ° C.
[00130] When the melt viscosity (Π1α ') is less than 1 x 10 ² Pa · s, narrowing and agitation of the film can be significant in the formation of the film by extrusion, such as lamination with melt coextrusion or melt extrusion, thereby intensifying the variation in thickness and reducing the width of the obtained multilayer structure and layer A, before lamination, and thus it may be impossible to obtain a multilayer structure that is uniform and has a desired size. In contrast, when the melt viscosity (Π1α ') is beyond 1 x 10 ⁴ Pa · s, cleavage of the film becomes likely to occur and high-speed film formability is noticeably deteriorated, particularly in the case where lamination with fusion coextrusion or fusion extrusion formation is carried out under conditions with high speed taking up exceeding 100 m / min, and swelling of the mold is likely to occur, whereby obtaining a thin multilayer structure or layer A before lamination can be difficult.
[00131] In addition, when the melting viscosity (Π2α ') is less than 1 x 10 ¹ Pa · s, narrowing and agitation of the film in the formation of
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44/158 film by extrusion, such as lamination with melt coextrusion or melt extrusion can be significant, thus increasing the thickness variation and reducing the width of the multilayer structure obtained and the layer A before lamination. On the contrary, when the melt viscosity (Q2a) is beyond 1 x 10 ³ Pa · s, a torque applied to the extruder becomes too high, and thus correcting the extrusion and welding line may be likely to be generated.
[00132] When a (1/2) logw (Γ ^ '/ η ^') value, calculated from the melting viscosity ratio (Γ ^ '/ η ^') is less than -0.8, the cleavage of film is likely to occur in extrusion film formation, such as fusion coextrusion or fusion extrusion lamination, whereby high-speed film formability can be deteriorated. On the other hand, when the value (1/2) logw (Γ ^ '/ η ^') is beyond -0.1, film narrowing and agitation occur in extrusion film formation, such as melting coextrusion lamination or fusion extrusion, with which variation in thickness and reduction in width can occur in the multilayer structure obtained and in layer A before lamination. In this respect, the value of (1/2) logw (η2Ά7η1Α) is more preferably not less than -0.6, and even more preferably not more than -0.2. It should be noted that the value (1/2) log10 (η2Ά7η1Α) in the above formula is determined in a natural logarithmic double graph of the melt viscosity along the ordinates in relation to the shear rate along the abscissa, as a slope of a line drawn through the connection of two points of the melting viscosity (η ^ ') and the melting viscosity (η2Α). In addition, the melt viscosity (η ^ ') and melt viscosity (η2Α) values, as referred to herein, are determined by a method described in the Examples below.
[00133] Also, when the resin has a high melting point, it is also preferred that the composition of layer A resin has
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45/158 a melting viscosity (ηι-) at a temperature of 220 ° C and a shear rate of 10 / s being not less than 1 x 10 P * if not more than 1 x 10 ⁴ Pa * s, and a melting viscosity (η ^ -) as determined at a temperature of 220 ° C and a shear rate of 1,000 / s being not less than 1 x 10 'Pa * if not more than 1 x 10' Pa * s, and the proportion (η1Α - / η1Α -) of the melting viscosity satisfies the following Formula (1A):
-0.8 <(1/2) log (η1Α - / η ^ -) <-0.1 (1A) [00134] When the melting viscosity (q-) is less than 1 x 10 P * s, provocation and agitation of film can be significant in the formation of the film by extrusion, such as lamination with fusion coextrusion or fusion extrusion, in this way intensifying the thickness variation and reducing the width of the obtained multilayer structure and layer A, before lamination, and thus can it is impossible to obtain a multilayer structure that is uniform and of the desired size. Conversely, when the melt viscosity (η1Α) is beyond 1 x 10 ⁴ Pa.s, cleavage of the film becomes likely to occur and the formability of high speed film is markedly deteriorated, particularly in the case where lamination with fusion coextrusion or fusion extrusion formation is carried out under conditions with high speed absorption exceeding 100 m / min, and mold swelling is likely to occur, so obtaining a thin multilayer structure or layer A before lamination can be difficult .
[00135] Furthermore, when the melt viscosity (η1Α -) is less than 1 x 10 Pa.s, tasting and shaking of the film in the formation of the extrusion film such as laminating with melting coextrusion or melting extrusion can be significant , thereby intensifying the thickness variation and reducing the width of the obtained multilayer structure and layer A before lamination. On the contrary, when
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46/158 melting viscosity (ηΐΑ -) is in addition to 1 x 10 Pa.s, a twist applied to the extruder becomes very high, and thus the plaster and the weld line can probably be generated, [00136] When a value (1/2) log (η1Α / η1Α) calculated from the ratio (η ^ / η1Α) calculated from the ratio of (η ^ / η1Α) melting viscosity is less than -0.8, the cleavage of the film is likely to occur in the formation of the film by extrusion, such as lamination with melt coextrusion or melt extrusion, so the formability of the high speed film may be deteriorated. On the other hand, when the value (1/2) log (η ^ / η1Α) is beyond -0.1, neck-in and film agitation occur in the formation of the film by extrusion such as lamination with fusion coextrusion or fusion extrusion, so the variation in thickness and the reduction in width can occur in the multilayer structure obtained, and in layer A before lamination. In this regard, the value of (1/2) log, (η ^ / η1Α) is more preferable not less than -0.6 and even more preferably not greater than -0.2. It should be noted that the value of (1/2) log (η ^ / η1Α) in the above formula is determined on a natural double logarithmic graph of the melt viscosity together with the ordinate with respect to the shear rate along with the abscissa, as an inclination of a drawn line connecting two points of the melting viscosity (η ^ -) and the melting viscosity (Q1a) and the melting viscosity (η ^ -). In addition, melt viscosity (η1Α) and melt viscosity (η1Α -) values, as referred to herein, are determined by a method described in the Examples below.
[00137] The resin composition of layer A preferably presents, in connection with a relationship between the melting time by kneading and the torque at at least one temperature point that is higher than its melting point by 10 to 80 ° C, a behavioral viscosity stability value (M100 / M20, where M20 repeats 870190056670, from 19/06/2019, page 50/172
47/158 preset a determined torque 20 minutes after starting kneading, and M100 represents a determined torque 100 min after starting kneading) falling within the range of 0.5 to 1.5. As the stability value of behavioral viscosity is approached to 1, superior thermal stability (long-term property) is indicated, with less change in viscosity.
Layer B [00138] Layer B consists of a resin composition containing a thermoplastic resin. Since layer B made of a resin composition containing thermoplastic resin is laminated, the multilayer structure may have improved elasticity and thermoformability. In addition, since the multilayer structure can enhance the adhesiveness between layers between layer B and layer A, high durability can be provided, and gas barrier properties and resilience can be maintained even if used with deformation.
[00139] Thermoplastic resin is not particularly limited, since it is a resin, it is softened to exhibit plasticity by heating to glass transition temperature.
[00140] A melting point, and is preferably at least one resin selected from the group consisting of thermoplastic polyurethane (hereinafter, it can also be referred to as TPU), polyamide, and an adhesive resin, presenting a functional group capable of reacting with a group included in the gas barrier resin, in the molecule (hereinafter it can also be referred to merely as adhesive resin. According to the multilayer structure, the use of a thermoplastic resin.
TPU [00141] TPU consists of a high molecular polyol, an organic polyisocyanate, a chain extender and the like. This hand polyol
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High lecular 48/158 is a substance that has a plurality of hydroxyl groups, and can be obtained by polycondensation, addition polymerization, (for example, ring opening polymerization), by polyaddition, or the like. Examples of the high molecular weight polyol include polyester polyol, polyether polyol, polycarbonate polyol, co-condensates thereof (for example, polyester-ether-polyol), and the like. This high molecular polyol can be used alone of one type, or as a mixture of two types of it. Of these, due to having a carbonyl group which reacts with a hydroxyl or similar group of the gas barrier resin in layer A, in this way capable of enhancing the adhesiveness between layers of the obtained multilayer structure, the polyester polyol or polycarbonate polyol is preferred, and polyester polyol is particularly preferred.
[00142] The polyester polyol can be produced, for example, according to a conventional method, allowing a dicarboxylic acid, an ester thereof or a conformable ester derivative, such as an anhydride thereof, to be condensed with a polyol of low molecular weight through a direct esterification reaction or a transesterification reaction, or by submitting lactone for ring opening polymerization.
[00143] The dicarboxylic acid that constitutes the polyester polyester of dicarboxylic acid is not particularly limited, and the dicarboxylic acid generally employed in the production of a polyester can be used. Specific examples of dicarboxylic acid include aliphatic dicarboxylic acids with 4 to 12 carbon atoms, such as succinic acid, glutaric acid, adipic acid, pyelic acid, submeric acid, azelaic acid, sebacic acid, dodecanedioic acid, methyl succinic acid, 2- methylglutaric acid, trimethyladipic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid and 3,7-dimethyldecanedioic acid; dicarboxylic alicyclic acids such as acid
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49/158 cyclohexanedicarboxylic; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid and naphthalenedicarboxylic acid, and the like. These dicarboxylic acids can be used alone of one type, or as a mixture of two types thereof. Of these, due to having a carbonyl group that can be more readily reacted with a hydroxyl group and similar to the gas barrier resin in layer A, and further intensifying the multilayer structure adhesiveness, aliphatic dicarboxylic acids with 6 to 12 carbon atoms are preferred, and adipic acid, azelaic acid or sebacic acid are particularly preferred.
[00144] The low molecular weight polyol that constitutes the polyester polyol is not particularly limited, and polyester polyol generally employed in the production of a polyester can be used. Specific examples of the low molecular weight polyol include aliphatic diols with 2 to 15 carbon atoms, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3propanediol, 1, 3-butylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 2, 7-dimethyl-1,8-octanediol, 1,9-nonanediol, 2-methyl1,9-nonanediol, 1,10-decanediol and 2,2-diethyl-1,3-propanediol; alicyclic diols such as 1,4-cyclohexanediol, cyclohexanedimethanol, cyclooctanedimethanol, and dimethylcyclooctanedimethanol; bivalent aromatic alcohols, such as 1,4-bis (p-hydroxyethoxy) benzene, and the like. These low molecular weight polyols can be used either alone of one type, or as a mixture of two types thereof. Among these, aliphatic diols having 5 to 12 carbon atoms and having a methyl group on the side chain such as 3-methyl-1,5-pentanediol, 2-methyl-1,8octanediol, 2,7-dimethyl-1,8- octanodiol, 1,9-nonanediol and 2,8-dimethyl-1,9nonanediol are preferred in terms of the ease of occurrence of the reaction of the ester group in the polyester polyol with a hydroxyl group and
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50/158 similar to the gas barrier resin in layer A, and the like, and the possibility of providing superior interlayer adhesiveness of the obtained multilayer structure. In addition, when two or more types of low molecular weight polyols are used as a mixture, it is more preferred that such an aliphatic diois having 5 to 12 carbon atoms and having a methyl group in the side chain is used in a proportion of not less than 50 mol% in relation to the total amount of the low molecular weight polyol. In addition, together with the low molecular weight polyol, a small amount of low molecular weight polyol having three or more functionalities can be used in combination. Examples of the low molecular weight polyol having three or more functionalities include trimethylolpropane, trimethylolethane, glycerin, 1,2,6-hexanotriol, and the like.
[00145] Examples of the lactone include ε-caprolactone, β-methyl-ovalerolactone, and the like.
[00146] Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (methylthetramethylene) glycol, and the like. These polyether polyols can be used either alone of one type, or as a mixture of two types thereof. Among these, polytetramethylene glycol is preferred.
[00147] Like polycarbonate polyol, for example, a product obtained by condensation polymerization of aliphatic diol with 2 to 12 carbon atoms, such as 1,4-butanediol, 1,5-pentanediol, 1,6hexanediol, 1, 8-octanodiol or 1,10-decanediol, or a mixture of these with diphenyl carbonate or phosgene can be used appropriately.
[00148] The lower limit of the average number of molecular weight of the high molecular weight polyol is preferably 500, more preferably 600, and even more preferably 700. On the other hand, the upper limit of the average number of molecular weight of the high polyol pePetição 870190056670, of 06/19/2019, p. 54/172
51/158 molecular weight is preferably 8,000, more preferably 5,000, and even more preferably 3,000. When the average molecular weight number of the high molecular weight polyol is below the lower limit described above, the miscibility with organic polyisocyanate is so high that the resulting TPU has lower resilience, with which dynamic characteristics, such as elasticity and thermoformability of the multilayer structure obtained may deteriorate. Conversely, when the average molecular weight number of the high molecular weight polyol is beyond the upper limit described above, miscibility with organic polyisocyanate is so low that mixing in the polymerization process can be difficult, and as a result, stable TPU production may fail as a result of the generation of blocks of gelatinous matter, and the like. It is to be noted that the average molecular weight number of the high molecular weight polyol is determined according to JIS-1577-K, which is an average molecular weight number calculated based on the hydroxyl value.
[00149] Organic polyisocyanate is not particularly limiting, and well-known organic diisocyanate generally employed in the production of TPU can be used. Examples of the organic diisocyanate include aromatic diisocyanate, such as 4,4'-diphenylmethanediisocyanate, tolylenediisocyanate, phenylenediisocyanate, xylylenediisocyanate, 1,5naphthene diisocyanate, 3,3'-dichloro-4 , 4'-diphenyl methanediisocyanate and toluylenediisocyanate; aliphatic or alicyclic diisocyanate, such as hexamethylenediisocyanate, isophoronadisocyanate, 4,4'-dicyclohexylmethanediisocyanate and xylylenediisocyanate hydride, and the like. Among these, in light of the possibility of improving the strength and flexural strength of the obtained multilayer structure, 4,4'-diphenylmethanediisocyanate is preferred. These organic diisocyanates can be used either one type alone, or in combination of two or more types thereof.
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52/158 [00150] Like the chain extender, any chain extender generally employed for the production of TPU can be used, and a low molecular weight compound having two or more active hydrogen atoms that can react with an isocyanate group in the molecule and having a molecular weight not exceeding 300 is properly used. Examples of the chain extender include diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6hexanediol, 1,4-bis (p-hydroxyethoxy) -benzene, 1,4-cyclohexanediol, bi (phidroxyethyl) terephthalate and xylylene glycol, and the like. Among these, depending on the elasticity and thermoformability of the multilayer structure obtained being more favorable, aliphatic diol with 2 to 10 carbon atoms is preferred, and 1,4-butanediol is particularly preferred. These chain extenders can be used either alone of one type, or as a mixture of two types thereof.
[00151] In a method for the production of TPU, the above mentioned high molecular polyol, organic polyisocyanate and chain extender are used for the production of TPU using a well-known urethane reaction technique, and any of a method of prepolymer and a one-shot method (central lubrication) can be used for production. Of these, melt polymerization carried out under a substantially solvent-free condition is preferred, and continuous melt polymerization carried out using a multi-screw extruder is particularly preferred.
[00152] In TPU, it is preferable that the ratio (isocyanate / (high molecular polyol + chain extender)) of the mass of the organic polyisocyanate to the total mass of the high molecular weight polyol and the chain extender is not greater to 1.02. When the ratio is beyond 1.02, the stability in long-term operation during forming can be deteriorated.
[00153] The nitrogen content of TPU can be determined by
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53/158 properly selecting the ratio between the high molecular weight polyol and the organic diisocyanate used, the content practically falls within the range of 1 to 7.
[00154]%. In addition, for the layer B resin composition, a suitable catalyst to accelerate the reaction of the organic polyisocyanate and the high molecular weight polyol can be used, if necessary.
[00155] TPU hardness is, in terms of edge hardness A, preferably 50 to 95, more preferably 55 to 90, and even more preferably 60 to 85. The use of TPU having a hardness within the above range is preferred, since a laminate structure that is superior in mechanical strength and durability, and presents excellent flexibility is obtained.
Polyamide [00156] Polyamide is a polymer with an amide group in the main chain, and is obtained by polycondensation of at least three-membered lactam, ω-amino acid or diamine polymerizable acid or similar. Specific examples of polyamide are polycapramide (nylon 6), poly-amino-heptanoic acid (nylon 7), poly-ω-aminonanoic acid (nylon 9), polyundecanoamide (nylon 11), polyilaurylactam (nylon 12), polyethylenediamine (adipamine) 26), polytetramethylene adipamide (nailon 46) polyiexamethylene adipamide (nailon 66), polyiexamethylene sebacamide (nylon 610), polyiexamethylene dodecamide (nylon 612), polyioatamethylene adipamide (nylon 86), polydecylmethylamine as well as polyamide methylene (also adipamide). / laurylactam (nylon 6/12), a copolymer of ω ainonanoic acid / caprolactam (nylon 6/9), a copolymer of adipate hexamethylenediamonium / caprolactam (nylon 6/66), a hexamethylenediamine copolymer / adipate 12 / lauryl hexamethylamine (12) , a copolymer of adipate hexamethylenediamonium / sebacate hexamethylenediamonium (nylon
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54/158
66/610), an adipate ethylenediamonium / adipate hexamethylenediamonium copolymer (26/66), an adipate / hexamethylenediamonium adipate / hexamethylenediamonium sebacate (nylon 6/66/610), polyamide, polyamide (polyamide), polyamide (polyamide), polyamide (polyamide), polyamide (6)). 6T nylon), an isophthalamide / teleftalamide hecamethylene (6I / 6T nylon) and the like.
[00157] Additionally, in the previous polyamide, aliphatic diamine having a substituent introduced for that purpose as 2,2,4- or
2,4,4-, trimethylexamethylenediamine, or aromatic diamine such as methylene dibenzylamine or m-xylylene diamine can be used as the diamine. Alternatively, modification of polyamide can be performed using them. In addition, aliphatic dicarboxylic acid having a substituent introduced for that purpose such as 2,2,4- or 2,4,4, -trimethyladipic acid, alicyclic dicarboxylic acid such as 1,4-cyclohexanediacarboxylic acid or aromatic dicarboxylic acid such as phthalic acid, xylylenedicarboxylic acid, aquil substituted terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid can be used as dicarboxylic acid. Alternatively, modification of polyamide can be performed using them.
[00158] Like polyamide, one type or a plurality of types of it can be used. Among the polyamide, in the light of multilayer structure adhesiveness, since the amide group in the polyamide is more likely to react with a hydroxyl group of the gas barrier resin in layer A and the like, a hexamethylene isophthalamide / teleftalamide copolymer (nylon 6I / 6T) is preferred. In the hexamethyleneisophthalamide / teleftalamide copolymer, a molar ratio (I / T) of isophthalic acid unit (I) / terephthalic acid unit (T) falls in the range of preferably 60/40 to 100/0 (molar ratio), and more preferably 65/36 to 90/10 (molar ratio). In addition, polyamide is preferably a caprolact copolymer. Petition 870190056670, 19/06/2019, p. 58/172
55/158 ma / laurylactam, i.e., polyamide containing 6/12 nailon as a major component is also preferred. While the ratio of the nylon 6 component (caprolactam component) and the nylon 12 component (laurylactam component) included in the polyamide are not particularly limited, the ratio of the nylon component 12 to the total mass of the polyamide is preferably 5 to 60% by weight, and more preferably 5 to 50% by weight. In addition, the relative viscosity of the polyamide is not particularly limited; however, in light of the further intensification of the adhesive force between layer A and layer B in the obtained multilayer structure, the relative viscosity is preferably 1.0 to 4.0.
[00159] Furthermore, polyamide, aliphatic polyamide is preferred in light of flexibility.
[00160] The lower limit of the amount of the polyamide terminal carboxyl groups is preferably 1 peq (equivalent) / g, more preferably 3 Meq / g, and even more preferably 5 Meq / g. On the other hand, the upper limit on the amount of terminal carboxyl groups is preferably 1000 Meq / g, more preferably 800 Meq / g, and even more preferably 600 Meq / g. by establishing the quantity of the terminal carboxyl groups to be included in the above range, the hydroxyl group of the barrier resin in layer A and the like can react with not only the amide group of the polyamide in layer B but also the terminal carboxyl group, in this way allowing layer A and layer B to be more rigidly connected, and in this way the adhesiveness between layers of the multilayer structure can be further improved. When the number of terminal carboxyl groups is less than the lower limit described above, the adhesion between layers of the multilayer structure can be deteriorated. Conversely, when the number of terminal carboxyl groups is beyond the upper limit described above, the strength of the multilayer structure may be deteriorated.
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56/158 rada. It should be noted that the amount of polyamide terminal carboxyl groups can be quantitatively determined by dissolving a polyamide sample in benzyl alcohol and titrating with a sodium hydroxide solution using phenolphthalein as an indicator. Adhesive Resin [00161] The adhesive resin has a functional group capable of reacting with a group included in the gas barrier resin in the molecule. Examples of the group included in the gas barrier resin include a hydroxyl group included in EVOH, etc., a starch group included in the polyamide resin, etc., an ester group in the polyester resin and the like. According to the multilayer structure which includes laminated layer B constituted with a resin composition containing the adhesive resin, elongation and thermoformability, can be improved. In addition, since a bonding reaction occurs at the interface between layer A and layer B, in this way capable of enhancing the adhesiveness in the multilayer structure, superior durability is provided, and the gas barrier and elongation properties can be maintained even if used with deformation.
[00162] The functional group capable of reacting with the group included in the gas barrier resin contained in layer A, is not particularly limited since it can react with a group included in the gas barrier resin, and illustrative examples include group craboxyl or anhydride group thereof, a carboxylated metal group, a boronic acid group, a boron-containing group that can be converted into a boronic acid group in the presence of water, an ester group, a urea group, a carbonate group, a ether group, an imino group, an acetal group, an epoxy group, an isocyanate group and the like. Of these, in light of the stickiness between the extremely upper layers between layer A and layer B, and particularly excellent durability of the obtained multilayer structure, a carboxyl group, a carPetition group 870190056670, of 06/19/2019, p. 60/172
57/158 metal boxylate, a boronic acid group, a boron-containing group that can be converted to a boronic acid in the presence of water, and an ester group are preferred.
[00163] The adhesive resin is exemplified by the polyolefin modified by carboxylic acid or a metal salt thereof, a thermoplastic resin having a boronic acid group or a boron containing group that can be converted into a boronic acid group in the presence of water , a vinyl ester-based copolymer, a polyester-based resin, an acrylic resin, a butyral resin, an alkyl resin, a polyethylene oxide resin, a cellulose-based resin, a cellulose-based resin melamine, a styrene-acrylate copolymer, a phenol-based resin, a urea resin, a melamine-alkyl resin, an epoxy resin, a polyisocyanate resin and the like. Alternatively, a modified product from such a resin or copolymer can also be used. In particular, in terms of significant intensification of the adhesiveness between layers, and particularly superior durability of the obtained multilayer structure, and also in terms of improving its elongation and thermoformability, polyolefin modified by carboxylic acid or metal salt thereof, a thermoplastic resin having a boronic acid group or a boron-containing group that can be converted to a boronic acid group in the presence of water, or a vinyl ester-based copolymer is preferred, and a carboxylic acid modified polyolefin is particularly preferred. Like the adhesive resin, one type or a plurality of types thereof can be used.
[00164] Carboxylic acid modified polyolefin is a polyolefin having a carboxyl group or an anhydride group thereof in the molecule. In the polyolefin metal salt modified by carboxylic acid, all or part of the carboxyl group and anhydride group of the same
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58/158 included in the polyolefin, or polyolefin having a carboxyl group or an anhydride group thereof in the molecule, are present in the form of a metal carboxylate group. Such carboxylic acid modified polyolefins or metal salts thereof can be used of one type or a plurality of types.
[00165] Carboxylic acid modified polyolefin can be obtained, for example, by letting an olefin-based polymer be chemically bonded (for example, by addition reaction, or graft reaction) to an unsaturated ethylenically carboxylic acid or an anhydride of it, etc., be copolymerized. Furthermore, the carboxylic acid modified polyolefin metal salt can be obtained, for example, by replacing all or a part of the carboxyl groups included in the carboxylic acid modified polyolefin with a metal ion.
[00166] When the polyolefin modified by carboxylic acid is obtained by letting an olefin-based polymer be chemically bound to an ethylenically unsaturated carboxylic acid or an anhydride thereof, the olefin-based polymer is exemplified by the polyolefin as polyethylene (low pressure , medium pressure, high pressure), linear low density polyethylene, polypropylene or polybutene; an olefin copolymer with a comonomer that is copolymerizable with the olefin (vinyl acetate, unsaturated carboxylate ester, etc.), for example, an ethyl acetate-ethylene vinyl copolymer, an ethylene-acrylic acid ethyl copolymer, and the like . Of these, in the light of significant improvement in adhesiveness, elongation and thermoformatility between layers in the multilayer structure obtained, linear low density polyethylene, an ethylene-vinyl acetate copolymer (vinyl acetate content: 5 to 55% by weight), or a copolymer ethyl ester of ethyleneacrylic acid (ethyl ester acrylate content: 8 to 35% by weight) is preferred, and linear low density polyethylene or an ethylene copolymer
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59/158 vinyl acetate (vinyl acetate content: 5 to 55% by weight) is particularly preferred.
[00167] In addition, unsaturated ethylenic carboxylic acid or an anhydride thereof to be chemically bonded to the olefin-based polymer is exemplified by unsaturated ethylenic monocarboxylic acid, unsaturated ethylenic dicarboxylic acid or an anhydride thereof, and the like. Alternatively, a compound derived from such a carboxylic acid by esterifying all or a part of carboxyl groups can also be used, and carboxylic acid modified polyolefin can be obtained by hydrolysis of the ester group after polymerization is complete. Specific examples of such compounds include maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic acid anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester and the like. Of these, due to having an anhydride acid group that can readily react with a hydroxyl group of EVOH, etc., which constitutes layer A, and the multilayer structure obtained presenting an upper layer adhesion, unsaturated ethylene dicarboxylic acid anhydride is particularly preferred , and as a specific compound, maleic anhydride is particularly preferred over olefin-based polymer. On the other hand, the higher imitate value of the amount of addition or graft yield (degree of modification) is preferable 15% by mass, and more preferable 10% by mass. When the amount of addition or the graft yield is less than the lower limit described above, the adhesion between layers can be less, and thus the durability of the multilayer structure can be deteriorated. Conversely, when the amount of addition or graft yield is beyond the upper limit described above, coloring of the resin composition can be significant, thus the appearance of the multilayer structure
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60/158 can be deteriorated.
[00168] In a method to let the unsaturated ethylenic carboxylic acid or an anhydride thereof be chemically bonded to the polymer-based olefin, through an addition reaction or a graft reaction, for example, a radical reaction is allowed in the presence of a solvent (xylene, etc.), and a catalyst (peroxide, etc.) and the like [00169] Furthermore, when the modified polyolefin pod carboxylic acid is obtained by copolymerizing aolefin with an unsaturated carboxylic acid or the like, i.e. , in the case where the carboxylic acid modified polyolefin is a copolymer of unsaturated olefin carboxylic acid, the olefin used is, in the light of the improvement of the elongation and thermoformability of the multilayer structure obtained, α-olefin such as ethylene, propylene or 1-butene is preferred, and ethylene is particularly preferred. On the other hand, the unsaturated carboxylic acid used is exemplified by acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, and the like. Of these, in light of being readily available, acrylic acid or methacrylic acid is particularly preferred. In addition, the unsaturated olefin carboxylic acid copolymer may contain another monomer except for the olefin and unsaturated carboxylic acid as a copolymerization component. Illustrative examples of such a monomer may include vinyl esters such as vinyl acetate such as vinyl acetate and vinyl propionate; unsaturated carboxylate esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate,
2-ethylexyl acrylate, methyl methacrylate, isobutyl methacrylate and diethyl metracrylate; carbon monoxide and the like.
[00170] The lower limit value of the unit content of unsaturated carboxylic acid in the unsaturated olefin carboxylic acid copolymer is preferably 2 mol%, and even more preferably Petition 870190056670, of 06/19/2019, pg. 64/172
61/158 t and 3 mol% in terms of unit content of unsaturated carboxylic acid with respect to all structural units in the copolymer. On the other hand, the upper limit value of the content of the unsaturated carboxylic acid unit is preferably 15 mol%, and even more preferably 12 mol%. When the content of the unsaturated carboxylic acid unit is less than the lower limit described above, the adhesion between layers may be lower, and thus the durability of the multilayer structure may be impaired. Conversely, when the content of the unsaturated carboxylic acid unit is beyond the upper limit described above, the coloring of the resin composition can be significant, thus the appearance of the multilayer structure can be deteriorated.
[00171] The unsaturated olefin carboxylic acid copolymer is preferably a polymer obtained by leaving the random copolymerization of olefin and unsaturated carboxylic acid or an anhydride thereof. In particular, a polymer obtained by leaving random copolymerization of ethylene and unsaturated carboxylic acid or an anhydride thereof is still preferred.
[00172] Illustrative examples of the metal ion to form the modified polyolefin metal salt of carboxylic acid include alkali metal ions such as lithium, sodium and potassium; alkaline earth metal ions such as magnesium and calcium; d-block metal ion such as zinc and the like. The degree of neutralization of the metal salt of the carboxylic acid modified polyolefin, that is, the proportion of metal carboxylate groups in the metal salt of the carboxylic acid modified polyolefin with respect to the total number of carboxyl groups and non-metal carboxylate groups. is particularly limited, but the lower limit value of the degree of neutralization is preferably 5 mol%, more preferably 10 mol%, and even more preferable 30 mol%. On the other hand, the value of the upper limit of the degree of neutralization
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62/158 is preferably 90 mol%, more preferably 80 mol%, and even more preferably 70 mol%. When the degree of neutralization is less than the lower limit described above, the adhesiveness between layers can be lower, and thus the durability of the multilayer structure can be deteriorated. On the contrary, the degree of neutralization is beyond the upper limit described above, the coloring of the resin composition can be significant, so the appearance of the multilayer structure can be deteriorated.
[00173] The lower limit value of the melt flow rate (MFR) (190 ° C, under a load of 2160 g) of polyolefin modified by carboxylic acid or a metal salt thereof is preferably 0.05 g / 10 min, more preferably 0.2 g / 10 min, and even more preferably 0.5 g / 10 min. On the other hand, the upper limit value of the melt flow rate is preferably 50 g / 10 min, more preferably 40 g / 10 min, and even more preferably 30 g / 10 min.
[00174] The thermoplastic resin having a boronic acid group or a boron-containing group that can be converted into a boronic acid group in the presence of water (hereinafter, it can also be referred to as a boronic acid derivative group) is a thermoplastic resin having a group of boronic acid represented by Formula (X) below in the molecule, or having a group containing boron that can be converted into a group of boronic acid in the molecule.
OH (X) [00175] The boron-containing group that can be converted to a boronic acid group in the presence of water is not particularly limited since the boron-containing group, which can be converted to acid in a boronic acid group in the presence of water attrPetition 870190056670, dated 06/19/2019, p. 66/172
63/158 instead of being subjected to hydrolysis, examples of which include boronic acid ester groups represented by Formula (XI) below, boronic acid anhydride groups (XII) below, boronic acid base represented by Formula (XIII) ) below, and the like. In this regard, the group containing boron that can be converted to boronic acid in the presence of water means a group that can be converted into a group of boronic acid in the presence of water, when subjected to hydrolysis in water, a mixed liquid of water and an organic solvent (toluene, xylene, acetone, etc.), or a 5% mixed liquid of aqueous boric acid solution and the organic solvent mentioned above, under conditions involving a reaction time of 10 min to 2 hours, and a reaction temperature from room temperature to 150 ° C.
OX (XD [00176] In Formula (XI) above, X and Y represent a hydrogen atom, an aliphatic hydrocarbon group (a linear or branched alkyl group or an alkenyl group having 1 to 20 carbon atoms, etc.), an acyclic hydrocarbon group (a cycloalkyl group or a cycloalkenyl group, etc.), or an aromatic hydrocarbon group (a phenyl group or a biphenyl group, etc.); X and Y can be the same or different; X and Y can be bonded, unless at least one of X and Y represents a hydrogen atom, and where the allyphatic hydrocarbon group, the acyclic hydrocarbon group or the aliphatic hydrocarbon group can have another group, for example, a hydroxyl group, a hydroxyl group carboxyl or a halogen atom or the like.
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64/158
(W
(ΧΠΙ)
OR
[00177] In Formula (XIII) above, R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an aliphatic hydrocarbon group (a linear or branched alkyl group or an alkenyl group having 1 to 20 carbon atoms, etc.) an alicyclic hydrocarbon group (a cycloalkyl group or a cycloalkenyl group, etc.), an aromatic hydrocarbon group (a phenyl group or a biphenyl group, etc.); R ¹³ , R ¹⁴ and R ¹⁵ can be the same or different; M represents an alkali metal or an alkaline earth metal; and wherein, the aliphatic hydrocarbon group, the alicyclic hydrocarbon group or the aromatic hydrocarbon group, other groups such as, for example, a hydroxyl group, a carboxyl group, a halogen atom or the like.
[00178] Specific examples of the boronic acid ester group represented by Formula (XI) above include a boronic acid dimethyl ester group, a boronic acid diethyl ester group, a boronic acid dibutyl ester group, dicyclohexyl acid boronic acid, a group of ethylene glycol ester of boronic acid, a group of propylene glycol ester of boronic acid (a 1,2-propanediol ester group of boronic acid, a 1,3-propanediol ester group of boronic acid), a neopentyl group boronic acid ester, a group of boronic acid catechol ester, a group of boronic acid glycerin ester, a group of trimethylolethane boronic acid ester, a group of diethane
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65/158 laminates boronic acid ester and the like. In addition, specific examples of the boronic acid base represented by Formula (XIII) above include boronic acid sodium base, boronic acid potassium base, boronic acid calcium base and the like.
[00179] The content of the boronic acid derivative group in the thermoplastic resin is not particularly limited, but in light of the intensification of adhesion between layers in the multilayer structure, the lower limit value of the boronic acid derivative group content with respect to constitutional units whole of the polymer that constitutes the thermoplastic resin is preferably 0.0001 meq (equivalent) / g, and more preferably 0.0001 meq / g. On the other hand, the upper limit value of the content of the group derived from boronic acid is preferably 1 meq / g, and more preferably 0.1 meq / g. When the content of the boronic acid derivative group is less than the lower limit described above, the adhesion between layers may be lower, and thus the durability of the multilayer structure may be impaired. Conversely, when the content of the boronic acid derivative group is beyond the upper limit described above, the coloring of the resin composition can be significant, so that the appearance of the multilayer structure can be deteriorated.
[00180] Examples of suitable base polymer of the thermoplastic resin having a derivable boronic acid group include olefin-based polymers such as polyethylene (ultra-low density, low density, medium density, high density), an ethylene methyl acrylate copolymer, a ethylene-ethyl acrylate copolymer, an ethylene-vinyl acetate copolymer, propylene and ethylene-propylene copolymer; styrene-based polymers such as hydrogenated polystyrene products, a styrene-acetonitrile copolymer, a styrene-acetonitrile-butadiene copolymer and a styrene-duene block copolymer (hydrogenated products of a copolymer
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66/158 styrene-isoprene-block, a styrene-butdiene copolymer, an ethylene-isoprene-styrene block copolymer, etc.); (meth) acrylic acid ester based on polymers such as polymethyl acrylate, polyethyl acrylate and polymethyl methacrylate; vinyl halide based on polymers such as polymethyl methacrylate; vinyl halide-based polymers such as polyvinyl chloride and polyvinylidene fluoride; semi-aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate; aliphatic polyesters such as polyvalerolactone, polycaprolactone, polyethylene succinate and polybutylene succinate and the like.
[00181] The melt flow rate (MFR) (value as measured at 230 ° C, under a load of 2160 g) of the thermoplastic resin having a boronic acid derivable group, is preferably 0.01 to 500 g / 10 min , and more preferably 0.1 to 50 g / 10 min. Such thermoplastic resins having a boronic acid derivable group can be used of one type or a plurality of types thereof.
[00182] Next, a typical method for producing the thermoplastic resin, featuring a derivable group of boronic acid, is explained. In a first production method, polymer-based oleophin having a derivable group of boronic acid is obtained by leaving a boronic compound and a boric acid trialkyl is obtained by leaving the borane complex and a boric acid trialkyl ester to react with a polymer olefin-based having a carbon-carbon double bond in a nitrogen atmosphere to give an olefin-based polymer having a boronic acid dialkyl ester group, followed by letting it react with water or an alcohol. In this production method, if an olefin-based polymer having a double bond at the termination is used as a base material, an olefin-based polymer having a derivable boronic acid group at the termination is obtained. Alternatively, when the olefin-based polymer has a double bond in the chain
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67/158 side and the main chain is used as a basic material, an olefin-based polymer having a derivative group of boronic acid in the side chain is mainly obtained.
[00183] Examples of typical production of the olefin-based polymer having a double bond which is a basic material include: 1) a method in which a common polymer-based olefin is used, and double bonds present in the termination in a slight amount Is it used; 2) a method in which a common polymer-based olefin undergoes thermal decomposition under oxygen-free conditions to obtain an olefin-based polymer having a double bond at the termination; and 3) a method in which a polymer-based oefin having a double bond is obtained by copolymerizing a monomer-based olefin and a monomer-based diene. In connection with method 1), a process for producing well-known olefin-based polymer can be employed, but a production method by means of a Phillips process, or a production method in which metallocene based on polymerization catalyst is employed. used as a polymerization catalyst, without using hydrogen as a chain transfer agent (eg, DE 4030399) is preferred. In connection with method 2), the olefin-based polymer can be obtained according to a well-known process (for example, see USP Nos. 2835659 and 3087922) to undergo thermal oxidation under oxygen-free conditions in an atmosphere of nitrogen or under a vacuum condition, at a temperature of 300 to 500 ° C. In connection with method 3) a production method (for example, see Japanese Unexamined Patent Application, Publication No. 550-44282, DE3021273) of an olefin-diene-based copolymer using a well-known Ziegler-type catalyst can be employed.
[00184] The borane complex that can be used in the previous one is
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68/158 preferably a borane-tetrahydrofuran complex, a borane-dimethyl sulfide complex, a borane-pyridine complex, a borane-trimethylamine complex, a borane-triethylamine complex and the like. Among these, a borane-dimethyl sulfide complex, a borane-trimethylamine complex, a boranotriethylamine complex are more preferred. The amount of a borane complex charged for the reaction preferably falls within the 1/3 equivalent range with respect to the total number of olefin-based polymer double bonds. In addition, the boric acid trialkyl ester is preferably a lower alkyl ester of boric acid such as trimethyl borate, triethyl borate, tripropyl borate or tributyl borate. The amount of boric acid trialkyl ester charged to the reaction preferably falls within the range of 1 equivalent to 100 equivalent with respect to the total number of olefin-based polymer double bonds. Although a solvent cannot be used in particular, in the case where a solvent is used, a solvent based on saturated hydrocarbon such as hexane heptane, ocatane, decane, dodecane, cyclohexane, ethylcyclohexane or decalin is preferred.
[00185] The reaction temperature of the reaction is carried out with the borane complex or boric acid trialkyl ester and the olefin-based polymer is normally from room temperature to 300 ° C, preferably 100 to 250 ° C. the reaction time is usually 1 min to 10 hours, and preferably 5 min to 5 hours.
[00186] Under the reaction conditions of the olefin-based polymer having a boronic acid diakyl ester, obtained as described above with water or alcohol, in general, an organic solvent such as toluene, xylene, acetone or ethyl acetate is used as a solvent reaction, and water; a monovalent alcohol such as methanol, ethanol or butanol; or a polyhydric alcohol such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, neopentyl glycol, glycerin, trimethylolmethane,
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69/158 pentaerythritol or dipentaerythritol is allowed to react in an amount from 1 to 100 equivalent, or more significantly in excess of the dialkyl ester group of boronic acid.
[00187] In a second method of production of the thermoplastic resin having a derivable group of boronic acid, the olefin-based polymer having a derivable group of boronic acid at the termination is obtained by submitting at least one selected from an olefin-based monomer, a vinyl-based monomer or a diene-based monomer for the polymerization of the radical in the presence of thiol having a derivable group of boronic acid.
[00188] The thiol, a derivative group of boronic acid that is a basic material can be obtained by letting a borane or diborane complex react with a thiol having a double bond in a nitrogen atmosphere, followed by the addition of alcohol or water. In this procedure, the thiol having a double bond is exemplified by 2-propene-1-thiol, 2-methyl-propene-1-thiol, 3-nutene-1-thiol, 4-pentene1-thiol, and the like. Of these, 2-propene-1-thiol or 2-methyl-2-propene-1-thiol is preferred. The borane complex used here can be similar to one of those described above, and of these, a borane-tetrahydrofuran complex or a borane-dimethyl sulfide complex is particularly preferably used. The amount of the borane or diborane complex added is preferably about 1 equivalent with respect to the thiol having a double bond. Under the reaction conditions, the temperature is preferably from room temperature to 200 ° C. The solvent is exemplified by ether-type solvents such as terahydrofuran (THF) and diglyme; saturated hydrocarbon type solvent such as hexane, heptane, ethylcyclohexane and decaline, and the like, and of these, tetrahydrofuran is preferred. An alcohol added after completing the reaction is preferably a lower alcohol having 1 to 6 carbon atoms such as methanol or ethanol, and particularly,
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70/158 methanol is preferred.
[00189] At least one selected from an olefin-based monomer, a vinyl-based monomer and a diene-based monomer is subjected to radical polymerization in the presence of the thiol having a derivative group of boronic acid thus obtained to obtain a polymer having a derivable group of boronic acid. For polymerization, an azo-based or peroxide-based initiator is commonly used. The polymerization temperature preferably is in the range of from room temperature to 150 ° C. The amount of thiol having an added boronic acid derivative group is preferably about 0.001 mmol to 1 mmol per gram of the monomer. Although a preferable thiol addition process is not particularly limited, but when a monomer that is likely to be chain-carrying transfers such used vinyl acetate or styrene, the thiol is preferably fed into the polymerization system during polymerization, whereas when a monomer that is hardly conducts chain transfer as methyl methacrylate is used, the thiol is preferably loaded beforehand into the polymerization system.
[00190] In a third production method of the thermoplastic resin having a boronic acid derivable group, the thermoplastic resin having a boronic acid derivative group in the side chain is obtained by leaving a monomer having a boronic acid derivative group to be copolymerized with at least a monomer selected from an olefin-based monomer, a vinyl-based monomer and a diene-based monomer. Examples of a monomer having a boronic acid derivable group in this procedure include 3-acryloylaminobenzenoboronic acid, ethylene glycol ester of 3-acryloylaminobenzenoboronic acid, 3methacryloylaminobenzenoboronic acid, ethylene glycol ester of 3- me acid
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71/158 tacryloylaminobenzenoboronic acid, 4-vinylphenylboronic acid, ethylene glycol ester of 4-vinylphenylboronic acid, and the like.
[00191] Alternatively, the thermoplastic resin having a derivative group of boronic acid in the side chain can be obtained, for example, by producing a random copolymer or an unsaturated carboxylic acid graft copolymer such as acrylic acid, methacrylic acid, itaconic acid, citraconic acid , fumaric acid, or maleic anhydride with at least one monomer selected from an olefin-based monomer, a vinyl-based monomer and a diene monomer, and subjecting the carboxyl groups contained in the polymer to an amidation reaction with boronic acid containing amino group or an ester of boronic acid containing amino group such as m-aminophenylbenzenoboronic or an ethylene glycol ester of m-aminophenylboronic acid, with or without using a condensing agent such as carbodiimide.
[00192] The vinyl ester based copolymer is a copolymer including at least 30 mol% or more vinyl ester units with respect to the entire structural units that make up the copolymer. When the proportion of the vinyl ester unit in the copolymer is less than 30 mol%, the adhesion between layers of the multilayer structure can be deteriorated. The ester vinyl is exemplified fatty acid vinyl esters such as vinyl acetate, vinyl formate, vinyl propionate and vinyl pilvalate. Of these, in light of being readily available, vinyl acetate is particularly preferred. In addition, illustrative examples of the copolymerization component that can be copolymerized with the vinyl ester in the vinyl ester based copolymer include olefins such as ethylene and propylene; styrenes such as styrene and pmethylstyrene; halogen containing olefins such as vinyl chloride, (meth) acryl esters such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate; dienos as bu
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72/158 tadiene and isoprene; unsaturated nitriles such as acrylonitrile, and the like. These copolymerization components can be used of one type or a plurality of types thereof. The glass transition point (Tg) of the vinyl ester copolymer can be adjusted by changing the type and quantity of the polymerization component. Specific illustrative examples of the vinyl ester-based copolymer include a copolymer of ethylene vinyl acetate acetate, a propylene vinyl acetate copolymer, a chloride vinyl vinyl copolymer, an acrylonitrile vinyl acetate copolymer, and the like. However, in the light of a special improvement in adhesiveness, elongation and thermoformability between layers of the obtained multilayer structure, a copolymer of ethylene vinyl acetate is particularly preferred.
[00193] The adhesive resin mentioned above mixed with another resin can also be used as the layer B resin composition. By mixing as another resin, the content of functional groups included in the layer B resin composition can be regulated, and the properties physical properties such as thermal stability, melt viscosity and adhesion to layer A, and the like, can be controlled.
[00194] It is necessary that such another resin has a characteristic capable of forming a laminate, and polyolefin is exemplified as a preferable resin. In particular, when the adhesive resin is obtained by modification, the other resin preferably has a monomer unit that is the same as the monomer unit of an unmodified adhesive resin. In other words, when, for example, the aforementioned carboxylic acid modified polyolefin is used as the adhesive resin, the unmodified polyolefin thereof is preferably used as the other resin (for example, use of a low density polyethylene blend linear modified by maleic anhydride and unmodified linear low density polyethylene, etc.). The proportion of the adhesive resin and the other resin can be
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73/158 selected ad libitum to meet the required performances, and the mass ratio of the adhesive resin / other resin is preferably 2/98 to 40/60.
[00195] Furthermore, in order to improve the moisture resistance of the multilayer structure, to include an alicyclic olefin polymer in the composition of layer B resin as another resin, it is also preferred. When the alicyclic olefin polymer is included in the layer B resin composition, the weight ratio of the adhesive resin / alicyclic olefin polymer is preferably 2/98 to 40/60, and more preferably 5/95 to 30/70.
[00196] The alicyclic olefin polymer is a polymer having a repeating unit that includes an alicyclic structure. The alicyclic structure is preferably a saturated cyclic hydrocarbon structure (cycloalkane), an unsaturated cyclic hydrocarbon structure (cycloalkene) and the like, in light of mechanical strength, heat resistance, etc., and a cycloalkane structure or a cycloalkene structure it is preferred, and a cycloalkane structure is the most preferred of these. Although the alicyclic structure may be present in the main chain or in the side chain, in the light of mechanical strength, heat resistance, etc., the alicyclic structure is preferably included in the main chain. The number of carbon atoms composing the alicyclic structure is not particularly limited, but when the number is in the range of normally 4 to 30, preferably 5 to 20, and more preferably 5 to 15, the characteristic features of such mechanical strength, strength the heat and formability of the resin-layer, etc. can be highly balanced.
[00197] The alicyclic olefin polymer may involve an acyclic olefin homopolymer and copolymer, and a derivative thereof (hydrogenated product, etc.). In addition, the polymerization process may involve addition polymerization or
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74/158 ring.
[00198] Examples of the alicyclic olefin polymer include a ring-opening polymer of a monomer having a norbonene ring (hereinafter also referred to as a norbonene monomer) and hydrogenated products thereof, addition polymers of a norbornene monomer , copolymers for adding a norbornene monomer and a vinyl compound, monocyclic cycloalkene addition polymers, conjugated alicyclic diene polymers, vinyl-based alicyclic hydrocarbon polymers and hydrogenated products thereof, and the like. In addition, polymers having an alicyclic structure formed by hydrogenation after polymerization, thus leading to include a structure equivalent to an alicyclic olefin polymer, such as hydrogenated aromatic ring products of an aromatic olefin polymer, are also involved. The alicyclic olefin polymerization process, and the hydrogenation process carried out as needed are not particularly limited, and can be carried out according to a well-known method.
[00199] In addition, the alicyclic olefin polymer also includes polymers having a polar group. The polar group is exemplified by a hydroxyl group, a carboxyl group, an alkoxyl group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amino group, an ester group, a carboxylic anhydride group and the like, and particularly a carboxyl group and a carboxylic anhydride group are suitable. Although the method for obtaining an alicyclic olefin polymer having a polar group is not particularly limited, and may include, for example, (i) a method in which an alicyclic olefin monomer having a polar group is subjected to homopolymerization or copolymerization with another monomer; (ii) a method in which graft polymerization of a poly
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75/158 mere alicyclic olefin not having a polar group is allowed with a compound containing unsaturated carbon-carbon ligand having a polar group, for example, in the presence of an initiator radical to introduce a polar group and the like.
[00200] The alicyclic olefin monomer having a polar group that can be used in method (i) is exemplified by the alicyclic olefin monomers containing carboxyl group as 8hydroxycarbonyl tetracycline (4.4.0.11) dodeca-3-eno, 5-
hydroxycaronylbicyclo [2.2.1] hept-2-ene, 5-methyl-5- hi droxicarbonilbiciclo [2.2.1] hept-2-eno,5-carboxymethyl-5- hi droxicarbonilbiciclo [2.2.1] hept-2-eno,8-methyl-8- hydroxycarboniltetracyclo [4.4.0.11] dodeca-3-ene, 5-exo-6-endo-hydro- xicarboni lbiciclo [2.2.1] hept-2-ene and 8 — exo-9-endo-
dihydroxycarboniltetracyclo [4.4.0.11] dodeca-3-ene, alicyclic olefin monomers containing anhydride acid group such as bicycles [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, tetracycline [4.4.0.11] dodeca-3 -eno-8,9-dicarboxylic anhydride and hexacyclo [6.6.1.TT '0' 0] heptadeca-4-ene-11,12-dicarboxylic anhydride; and the like.
[00201] Specific examples of the monomer to obtain alicyclic olefin polymer not having a polar group that can be used in method (ii) include bicyclic [2.2.1] hetp-2-ene (common name: norbo neno), 5-3ti l-bi cycle [2.2.1] hept-e-ene, 5-buti l-bicyclo [2.2.1] hept-2-ene,
5-ethylidene-bicycles [2.2.1] hept-2-ene, 5-methylidene-bicycles [2.2.1] hept-2ene, 5-vinyl-bicycles [2.2.1] hept-2-ene, tricycle [4.3. 0.1 ''] deca-3,7-diene (common name: dicyclopentadiene), tetracycline [8.4.0.Τ '0'] tetradeca3,5,7,12,11-tetraene, tetracycline [4.4.0.11 '] dodeca- 3-ene (common name: tetracyclododecene), 8-methyl-tetracycle [4.4.0.1 1 '] dodeca-3-ene, 8-ethylthetracyclo [4.4.0.11'] dodeca-3-eno, 8-methylidene-tetracyclo [4.4 .0.11 '] dodeca-3-eno, 8-ethylidenePetition 870190056670, of 6/19/2019, p. 79/172
76/158 tetracycle [4.4.0.1 1 '] dodeca-3-ene, 8-vinyl-tetracycle [4.4.0.1 1'] dodeca-
3-ene, 8-propenyl-tetracycle [4.4.0.1 1 '] dodeca-3-ene, pentacycle [6.5.1.1' O''0 '] pentadeca-3,10-diene, pentacycle [7.4.0.1.'1 '' 0 '] pentadeca-4-11- diene, cyclopentene, cyclopentadiene, 1,4-methane-1,4,4a, 5,10,10ahexa-hydroanthracene, 8-phenyl-tetracyclo [4.4.0.11'] dodeca- 3-ene and the like.
[00202] Furthermore, the compound containing unsaturated carbon-carbon bond having a polar group that can be used in method (ii) is exemplified by the unsaturated carboxylic acid compounds such as acrylic acid, methacrylic acid, α-ethylacrylic acid, 2-acid hydroethyl (meth) acrylic, maleic acid, fumaric acid, itaconic acid, endocis-bicyclo acid [2.2.1] hetp-5-ene-2,3-dicarboxylic acid and methyl-endocis-bicyclo acid [2.2.1] hetp-5 -eno-2,3-dicarboxylic; unsaturated carboxylic anhydrides such as maleic anhydride, chloromaleic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride and citraconic anhydride; and the like.
[00203] The method for mixing the adhesive resin with another resin is not particularly limited since the mixture can be homogeneously mixed, and dry mixing carried out in a solid state, or molten mixture with a melt extruder pelletizing a mixture obtained by dry mixing can be employed. Illustrative examples of means for melting the mixture include methods performed using a mixture and include methods performed using a strip mixer, a coamassador mixer, a pelletizing machine, mixing rolls, an extruder or an intensive mixer. Of these, in light of the simplicity of the steps and costs, a single or twin screw extruder is preferably used. The temperature of the mixture is appropriately selected depending on the properties of the installation, the type of resin, proportions of the mixture and the like, and can be in the range of 150 to 300 ° C in many cases. In addition, when a mul structure
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77/158 layers are formed, molten kneading can be performed using an extruder coupled to a forming machine.
[00204] The layer B resin composition may contain a variety of additives such as a resin other than a thermoplastic resin, or a heat stabilizer, an ultraviolet ray absorber, an antioxidant, a dye and a filler , in the range not to compromise the object of the present invention. When the layer B resin composition contains an additive, the amount thereof is preferably not more than 50% by weight, more preferably not more than 30% by weight, and is preferably not more than 10% by weight in relation to the amount total resin composition.
[00205] For reasons similar to those described above in connection with the layer A resin composition, it is preferred that a melt viscosity (Q1b) of the layer B resin composition, as determined at a temperature of 210 ° C and a rate shear rate of 10 / s is less than 1 x 102 Pa · s and not more than 1 x 104 Pa · s, and a melting viscosity (Π2β) as determined at a temperature of 210 ° C and a shear rate of 1,000 / s of the same is not less than 1 x 10 ¹ Pa • if not more than 1 x 10 ³ Pa • s, and a proportion (Π2β / Π1β) of the melting viscosity satisfies the following Formula (1B):
-0.8 <(1/2) log10 (Π2β / Π1β) <-0.1 (1B).
[00206] In addition, for reasons similar to those referred to under layer A, the value (1/2) log10 (Π2β / Π1β) is more preferably not less than -0.6, and even more preferably not more than -0 ,2.
[00207] For reasons similar to those described above in connection with the layer A resin composition, at a temperature higher than the Vicat softening temperature of the layer A or layer B resin composition by 30 ° C, the composition of the resi
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78/158 in layer A and / or layer B has a melting viscosity (γ | 2β) as determined at a shear rate of 10 / s being not less than 1 x 10 Pa · if not more than 1 x 10 ' Pa · s, and a proportion (r | 2B / r | 1B) of the melting viscosity satisfies the following formula (1B '):
-0.8 <(1/2) log10 (r ^ / M <-0.1 (1B ').
[00208] Furthermore, for reasons similar to those in connection with layer A, the value (1/2) log (r2B · / rw) is more preferably not less than -0.6 and even more preferably not more than -0.2. It should also be noted that the appropriate ranges in connection with that melting viscosity (r) and (r), and the ratio (r2B · / rw) of the melting viscosity may be particularly appropriate applied in the case where a softening temperature of Vicat of the resin composition of layer A or layer B is not less than 180 ° C.
[00209] Furthermore, when a melting point of the resin is very high, for reasons similar to those described above in connection with the composition of layer A resin, it is preferred that the composition of layer B resin has a melting viscosity (r) and the shear rate of 10 / sec is not less than 1 x 10 Pa · if not more than 1 x 10 Pa · if a melting viscosity (r) as determined at a temperature of 210 ° C and a rate shear rate of 1,000 / s being not less than 1 x 10 Pa · s and not more than 1 x 10 Pa · s, and a proportion (r ^ B · / rw) of the melting viscosity that satisfies Formula (1B '') Next:
-0.8 <(1/2) logw (r2B '' / r1B ··) <-0.1 (1B ··).
[00210] Also, for reasons similar to those in connection with layer A, the value (1/2) log (r '' / r '') is preferably not less than 0.6, and more preferably not more than -0 ,2.
Metal Salt [00211] At least one of the resin compositions included in the
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79/158 layer A and layer B, which are adjacent to each other contain a metal salt. Thus by including a metal salt in at least one of layers A and layer B, which are adjacent to each other, much higher adhesion between layers is much higher between layer A and layer B can be achieved. Due to such much superior adhesion between layers, the multilayer structure has superior durability. Although the reason for the improved adhesion between layers of the metal salt is not necessarily clear, it is believed that the improvement would result from the acceleration of a reaction forming a bond that occurs between the gas barrier resin in the layer A resin composition. , and the thermoplastic resin, in the layer B resin composition, due to the presence of the metal salt, and the like. As such a bonding reaction, a hydroxyl group exchange reaction that occurs between a TPU carbamate group or an amino group, etc., of poiamide with a hydroxyl group, etc., of the gas barrier resin, a reaction of addition of a hydroxyl group, etc., of the gas barrier resin to an isocyanate group remaining in TPU, an amide production reaction of a polyamide terminal carboxyl group with an EVOH hydroxyl group, also with another bonding reaction that occurs between the gas barrier resin and the adhesive resin, and the like can be assumed. It should be noted that the metal salt can be included in both the layer A resin composition and layer B resin composition, or in either layer A resin composition or layer B resin composition.
[00212] Although the metal salt is not particularly limited, an alkali metal salt, an alkaline earth metal salt or a metal block d metal salt listed in group 4 of the periodic table is preferred since interlayer adhesiveness can be further improved. Among these, an alkali metal salt or a metall salt 870190056670, dated 06/19/2019, p. 83/172
80/158 such an alkaline earth is most preferred, and an alkali metal salt is particularly preferred.
[00213] The alkali metal salt is not particularly limited, and its examples include salts of aliphatic carboxylic acids, salts of aromatic carboxylic acids, phosphoric acid salts, lithium, sodium, potassium metal complexes, etc., and others similar. Specific examples of the alkali metal salt include sodium acetate, potassium acetate, sodium phosphate, lithium phosphate, sodium stearate, potassium stearate, a sodium salt of ethylenediamine tetra acetic acid, and the like. Among these, sodium acetate, potassium acetate and sodium phosphate are particularly preferred, because they are readily available.
[00214] The alkaline earth metal salt is not particularly limited, and examples thereof include salts of acetic acid or salts of phosphoric acid of magnesium, calcium, barium, beryllium, or the like. Among these, acetic acid salts or magnesium or calcium phosphoric acid salts are particularly preferred, because they are readily available. To include such an alkaline earth metal salt it is also advantageous in terms of the ability to reduce the amount of adhesion to a mold of a resin forming machine generated by heat during the melting formation.
[00215] Although the metal salt of a block d metal listed in group 4 of the periodic table is not particularly limited, examples of it include salts of carboxylic acids, phosphoric acid salts or acetylacetonate salts of titanium, vanadium, chromium, manganese , iron, nickel, cobalt, copper, zinc, etc., and the like.
[00216] The lower limit of the content of the metal salt (content in terms of metal equivalent element on the basis of the entire multilayer structure) is 1 ppm, more preferably 5 ppm, even more preferably 10 ppm, and especially preferably 20 ppm. Per
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81/158 on the other hand, the upper limit of the metal salt content is 10,000 ppm, more preferably 5,000 ppm, even more preferably 1,000 ppm, and especially preferably 500 ppm. When the content of the metal salt is below the lower limit described above, the interlayer stickiness may be less, and thus the durability of the multilayer structure may be impaired. Conversely, when the content of the metal salt is beyond the upper limit described above, the coloring of the resin composition can be significant, with which the appearance of the internal multilayer structure can be deteriorated.
[00217] Metal salt may be included in the layer A or layer B resin composition by any method, which is not particularly limited, and a method similar to that for including a phosphate compound or similar in the layer resin composition A as described above can be employed.
Oxygen Purification Receiver [00218] The compositions that make up layer A and layer B may contain, in addition to containing the aforementioned metal salt and the like, any of the various components. As such a component, for example, an oxygen clearance receiver can be included. The oxygen clearance receptor component can be particularly used appropriately when the deposition of resin constituting the Bb layer includes the adhesive resin. The oxygen scrubber receiver can be contained in one of the resin compositions that make up layer A or layer B, it is preferably contained in the composition of layer A.
[00219] The clearance receptor is a substance with an oxygen clearance capability (oxygen absorbing function).
The ability of the oxygen clearance receiver, as referred to to mean a function of oxygen absorption and consumption in a given environment, or decrease in the amount of oxygen. The receiver
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82/158 of oxygen clearance that can be contained in the resin composition is not particularly limited to one that has such properties. By containing the oxygen clearance receiver in the resin composition, the gas barrier properties of the multilayer structure can be further improved as a result of the addition of the oxygen clearance receiver capability. As the oxygen clearance receptor, several types of substances can be used, examples of which include organic oxygen clearance receptors such as a thermoplastic resin having a clearance receptor or ascorbic acid capacity; inorganic oxygen clearance receptors such as iron or sulfuric acid salt, and the like. Of these, a thermoplastic resin having an oxygen clearance receptor capability is preferred, since superior oxygen clearance receptor property is provided, and it can be easily contained in the resin composition of the multilayer structure.
Thermoplastic Resin with Oxygen Clearance Receiving Capacity [00220] Thermoplastic resin with an oxygen clearing reception capacity is not particularly limited, since a thermoplastic resin capable of oxygen clearance, and examples include unsaturated hydrocarbon polymer based on ethylene having a carbon-carbon double bond or polymer blends (instead of those having a molecular weight not exceeding 1,000 and having a conjugated double bond), hereinafter they can also be referred to merely as a hydrocarbon polymer unsaturated and the like.
Unsaturated Hydrocarbon Polymer [00221] The unsaturated hydrocarbon polymer can have a substituent, or it can be unsubstituted. InsaPetition hydrocarbon polymer 870190056670, dated 06/19/2019, p. 86/172
83/158 unsubstituted tured is defined as an arbitrary compound having at least one aliphatic carbon-carbon double bond and consisting of 100% by weight of carbon and hydrogen in total. In addition, the substituted unsaturated hydrocarbon polymer is defined as an ethylene-based unsaturated hydrocarbon having at least one carbon-carbon aliphatic double bond and including about 50 to 99% by weight of carbon and hydrogen in total. Unsubstituted or substituted unsaturated hydrocarbon polymer has at least two ethylene-based unsaturated groups per molecule. More preferably, the substituted or unsubstituted saturated hydrocarbon polymer is a polymer compound having at least two ethylene-based unsaturated groups, and a mass average molecular weight of 1,000 or more. The polymer blend of the unsaturated hydrocarbon based on ethylene can be composed of a mixture of 2 types or more types of unsaturated hydrocarbons based on substituted or unsubstituted ethylene.
[00222] Examples of preferred unsubstituted unsaturated hydrocarbon polymers include the following diene polymers such as, for example, polyisoprene (e.g., trans-polyisoprene), polybutadiene (in particular, 1,2-polybutadiene, which is defined as polybutadiene having or greater than 50% of 1,2-fine structure), and copolymers of the same, for example, styrene-butadiene, but not limited to that purpose. Such a hydrocarbon also includes: polymer compounds, for example, polypentamers, polyoctamers, and other polymers produced by double olefin decomposition; oligomer diene, such as squalene; and polymers or copolymers derived from dicyclopentadiene, norbodiene, 5-ethylidene-2-norbonene, or another monomer that includes at least two carbonocarbon double bonds (conjugated or unconjugated). These hydrocarbons still involve carotenoids, for example, β-carotene.
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84/158 [00223] Preferred substituted unsaturated hydrocarbon polymer may include those having an oxygen-containing moiety, such as, ester, carboxylic acid, aldehyde, ether, ketone. Alcohol, peroxide, and / or hydroperoxide, but not limited to that. Specific examples of such hydrocarbons include condensed polymers such as, for example, polyesters derived from a monomer that includes a carbon-carbon double bond; unsaturated fatty acids such as oleic acid, ricinoleic acid, ricinoleic hydrating acid and linoleic acid, and derivatives thereof, such as, but not limited to, esters. Hydrocarbons can involve (meth) (meth) allyl acrylate.
[00224] In the unsaturated hydrocarbon polymer, the carbon-carbon double bond content is preferably 0.01 and 1.0 equivalent with respect to 100 g of the polymer. When the content of double bonds in the polymer is limited to being included in a range, both the property of the oxygen clearance receiver and the physical property of the multilayer structure can be maintained to be superior.
[00225] The polymer thus including decreased double bonds can be a blend of homopolymer, copolymer and / or polymer. A polymer blend is particularly desirable since a change in physical properties in a discontinuous phase has comparatively small influences on the entire physical properties of the blend which predominantly has a continuous phase, and thus it is desired that a majority of the existing double bonds included in the discontinuous phase.
[00226] Suitable examples of the homopolymer include poly (octamer) having 0.91 equivalent of double bonds in 100 g of the polymer, and oli (4-vinylcyclohexane) having 0.93 equivalent of double bonds in 100 g of the polymer. Copolymer Examples
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Appropriate 85/158 include C-C: alkyl alkylate and methacrylate. Other examples include copolymers derived from 1,3-butadiene, isoprene, 5-ethylidene-2-norbonene, 4-vinylcyclohexane, 1,4-hexadiene, 1,6ocatadiene or the like with one or two or more types of vinyl monomers such as, for example, ethylene, propylene, styrene, vinyl acetate, and / or α-olefin. Specific examples include ethylene, propylene and 5-ethylidene-2-norbonene terpolymers. Such EPDM elastomers typically contain 3 to 14% by weight of 5-ethylidene-2-norbonene. These polymers act according to the requirements mentioned above for double bonds, that is, they fall within the range of 0.01 to 1.0 equivalent in 100 g of the polymer. In addition, unsaturated polymers based on partially hydrogenated ethylene (e.g., butadiene), which includes at least about 50% hydrogenated double bonds, are suitable. Exemplary polymer blend can vary widely. Blends of EPDM and 20 to 40% polybutadiene, blends of EPDM and 20 to 40% poly (octonamer), and blends of polybutadiene and saturated polyolefin at 50/50 are particularly preferred.
Thermoplastic Resin Featuring Double Bonds of CarbonCarbon Substantially in Only the Main Chain [00227] Among the unsaturated hydrocarbon polymers mentioned above, in light of the much higher oxygen receptor properties and the possibility of being included in the resin composition of the multilayer structure, thermoplastic resins presenting carbon-carbon double bonds substantially only in the main chain (hereinafter, may be referred to merely as thermoplastic resin having double bonds), except for those having a molecular weight not exceeding 1,000 and having conjugated double bonds, are particularly preferred. In this regard, thermoplastic resin having carbon-carbon double bonds substantially only on the main chain), as mentioned here in
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86/158 feels, means that the carbon-carbon double bonds existing in the main chain of the thermoplastic resin represents not less than 90% of all carbon-carbon double bonds included in the main or side chain of the molecule. The carbon-carbon double bonds in the main chain account for preferably not less than 93%, and more preferably not less than 95%. [00228] Since the thermoplastic resin having double bonds have carbon-carbon double bonds in the molecule of the same, it can be efficiently reacted with oxygen, in this way superior capacity for receiving oxygen clearance can be achieved. By including such a thermoplastic resin in the resin composition, the gas barrier properties of the multilayer structure can be significantly improved. The carbonocarbon double bond involves conjugated double bonds, but does not involve multiple bonds included in an aromatic ring.
[00229] The lower limit of the content of carbonocarbon double bonds included in the thermoplastic resin having double bonds is preferably 0.001 equivalent / g, more preferably 0.005 equivalent / g, and even more preferably 0.01 equivalent / g. On the other hand, the upper limit of the carbonocarbon double bond content is preferably 0.04 equivalent / g, more preferably 0.03 equivalent / g, and even more preferably 0.02 equivalent / g. When the carbon-carbon double bond content is lower than the lower limit described above, the multilayer structure obtained may have the function of receiving insufficient oxygen clearance. On the contrary, when the content of carbon-carbon double bonds is beyond the upper limit described above, the coloring of the resin composition can be significant, in this way the appearance of the obtained multilayer structure can be deteriorated.
[00230] As described in the previous, the thermoplastic resin presents
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87/158 having double bonds due to having carbon-carbon double bonds substantially only in the main chain, accompanied by significantly less generation of decomposed matter presenting low molecular weights produced by cleaving side chain double bonds through an oxygen reaction. Although a portion of the decomposed matter having low molecular weights is an unpleasant odor substance, the development of an unpleasant odor can be minimized when such decomposed matter is less likely to be generated. In this way, including such a thermoplastic resin in the resin composition, a multilayer structure can be provided showing superior gas barrier properties and durability, while preventing the development of unpleasant odor, through oxygen clearance. In this regard, when a thermoplastic resin having many of the carbon-carbon double bonds in the side chain is used, the clearance receptor properties can be satisfactory; however, the decomposed matter is generated by cleaving the double bonds in the side chain as described above. In this way, the unpleasant odor is developed in this way the surrounding environment can be significantly compromised.
[00231] In thermoplastic resin with double bonds, when the carbon-carbon double bond in the main chain reacts with oxygen, oxidation occurs at an ally carbon site (carbon adjacent to the double bond); in this way, the allyl carbon is preferably different from the quaternary carbon. Furthermore, since it will be possible to generate decomposed matter having low molecular weights even if the main chain is cleaved, the allyl carbon is preferably an unsubstituted carbon, that is, methylene carbon in order to prevent this event. From the above considerations, the thermoplastic resin with double bonds is preferable
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88/158 has at least one of the units represented by the
Formulas (X) and (I) below:
R ¹⁸ R ¹⁹
CXV)
[00232] In the formulas above (XIV) and (XV), R ¹³ , R ¹⁴ and R ¹⁵ each independently represents a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, a alkylaryl group that may have a substituent, -COOR, -OCOR, a cyano group or a halogen atom; R and R can form a ring by means of a methylene group or an oxymethylene group, unless R and R both represent a hydrogen atom; R and R represent an alkyl group that may have a substituent, an aryl group that may have a substituent or an arylalkyl group that may have a substituent.
[00233] When R, R, R and R represent an alkyl group, the alkyl group preferably has 1 to 5 carbon atoms; when they represent an aryl group, the aryl group preferably has 6 to 10 carbon atoms; and when they represent an alkylaryl group, the alkylaryl group preferably has 7 to 11 carbon atoms. Specific examples of an alkyl group include a methyl group, an ethyl group, a propyl group and a phenyl group; examples of the alkylaryl group include a tolyl group; and examples of the atom of
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89/158 halogen includes a chlorine atom.
[00234] The substituent that can be included in the thermoplastic resin having double bonds is exemplified by several types of hydrophilic groups. The hydrophilic group as referred to herein is exemplified by a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an amino group, an aldehyde group, a carboxyl group, a metal carboxylate group, an epoxy group, an ester group, a carboxylic anhydride group, a boronic acid group, a boron-containing group that can be converted to a boronic acid group in the presence of water (for example, boronic acid ester group, a boronic acid anhydride group, a boronic acid based, etc.), and the like. Among this hydrophilic group, an aldehyde group, a carboxylic group, a metal carboxylate group, an epoxy group, an ester group, a carboxylic anhydride group, a boronic acid group, a group containing boron that can be converted into a group of boronic acid in the presence of water is preferred in terms of its ability to react with a hydroxyl group, etc., from EVOH. When the thermoplastic resin having double bonds includes as a hydrophilic group, the thermoplastic resin has high dispersibility in the composition of the resin, thus leading to the improvement of the oxygen clearance reception function of the obtained multilayer structure. In addition, along with this phenomenon, the adhesiveness between layers is improved as a result of the formation of a chemical bond through a reaction of this hydrophilic group with a hydroxyl group, a functional group or similar of EVOH in the adjacent layer, and characteristics such as properties of gas barrier and durability of the resulting multilayer structure are further improved.
[00235] In addition, thermoplastic resins having double bonds described in the previous one, compounds having the unit
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90/158 represented by Formulas (XIV) and (XV) above, in which R, R, R and R all represent a halogen atom are particularly preferred in light of odor prevention. Although the reason for prevention is not necessarily clear, it is assumed that when R, R, R and R do not represent a hydrogen atom but a listed group, the group can be oxidized and cleaved to convert to an odor substance when the thermoplastic resin reacts with oxygen.
[00236] In the thermoplastic resin having double bonds, the unit represented by Formulas (XIV) and (XV) above is preferably a unit derived from a diene compound. When the unit is derived from a diene compound, the thermoplastic resin having such a structural unit can be readily produced. The diene compound is exemplified by isoprene, butadiene, 2-ethylbutadiene, 2-butyl-butadiene, chloroprene and the like. Only one of these can be used alone, or a plurality of types can be used in combination. Examples of thermoplastic resins having double bonds include such a unit derived from a diene compound include polybutadiene, polyisoprene, polychloroprene, polyoctenylene, and the like. Of these, polybutadiene and polyoctenylene are particularly preferred in light of the particularly superior oxygen clearance function. Alternatively, a copolymer including as with a copolymerization component, a structural unit instead of the structural units mentioned above can also be used as the thermopolastic resin having double bonds. The polymerization component is exemplified by styrene, acrylonitrile, propylene, and the like. When the thermoplastic resin having double bonds is like a copolymer, the content of the units represented by Formulas (X) and (XI) above is preferably not less than 50 mol%, and more preferably not less than 70 mol% in terms of the total number of units with
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91/158 in relation to the entire structural units of the thermoplastic resin.
[00237] The lower limit of the average molecular weight of the thermoplastic resin having double bonds is preferably 1,000, more preferably 5,000, even more preferably 10,000, and particularly preferable 40,000. On the other hand, the upper limit of the average number molecular weight is preferably 500.00, more preferably 300,000, even more preferably 250.00, and particularly preferably 200,000. When the thermoplastic resin with double bonds has a molecular weight of less than 1,000, or greater than 500,000, the multilayer structure obtained can be involved in the lower forming processability and handling quality, and mechanical properties of the multilayer structure, such as strength and extensibility, can deteriorated. Furthermore, the dispersibility in the resin composition is decreased, and as a result, the gas barrier properties and clearance reception performance of the multilayer structure can be deteriorated. Thermoplastic resin having double bonds can be used of one type or of a plurality of types thereof.
[00238] The method for producing thermoplastic resin having carbon-carbon double bonds substantially only in the main chain, as described above, may vary depending on the type of thermoplastic resin and, for example, polybutadiene (cis-1,4polybutadiene) can be synthesized using a cobalt-based or nickel-based catalyst as a catalyst. Specific examples of the catalyst include a combination of a CoC1 2C-H * N complex and diethyl aluminum chloride, and the like. The solvent that can be used includes an inert, and in particular, organic hydrocarbon solvent having 6 to 12 carbon atoms such as an alicyclic hydrocarbon such as hexane, heptene, ocatane or decane, or an aromatic hydrocarbon such as toluene, benzene or xylene
Petition 870190056670, of 06/19/2019, p. 95/172
92/158 is appropriate. Polymerization is usually carried out at a temperature in the range of -78 ° C to 70 ° C for a period of time within the range of 1 to 50 hours.
[00239] It should be noted that the carbonocarbon double bonds that exist after completing the polymerization can be reduced by hydrogen in part in the range to not impart mechanical properties of the multilayer structure, and effects such as gas barrier properties and receptor performance debugging, and the like. In this procedure, it is preferred that in particular the carbon-carbon double bonds remain in the side chain, in particular they are selectively reduced by hydrogen.
Metal Salt Transition [00240] The resin composition preferably contains, in addition to the unsaturated hydrocarbon polymer mentioned above (including the thermoplastic resin having double bonds), still a transition metal salt (instead of the metal salts described above) ). When such a transition metal salt is included together with the unsaturated hydrocarbon polymer, the oxygen clearance receptor function of the obtained multilayer structure can be further improved, and as a result, additional upper gas barrier properties can be provided. It is believed that this event results from the acceleration by the transition metal salt of the reaction of the unsaturated hydrocarbon polymer with the oxygen present within the multilayer structure or oxygen going to permeabilize the multilayer structure.
[00241] A transition metal ion that constitutes the transition metal salt is exemplified by each ion of iron, nickel, copper, manganese, cobalt, rhodium, titanium, chromium, vanadium, ruthenium or similar, but not limited to them . Of these, each iron, nickel, copper, manganese or cobalt ion is preferred, each manganese or cobalt ion is preferred, each manganese or cobalt ion is more preferred, and
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93/158 cobalt ion is particularly preferred.
[00242] A counter anion of the transition metal ion that constitutes the transition metal salt is exemplified by the carboxylic acid ion or halogen anion, and the like. Specific examples of anion cotra include: anions generated by the ionization of a hydrogen ion of acetic acid, stearic acid, acetyl acetone, dimethyldithiocarbamic acid, palmitic acid, 2-ethylexanoic acid, neodecanoic acid, linoleic acid, tol acid, oleic acid, acid resin, capric acid, naphthenoic acid or the like; a chloride ion and an acetyl acetonate ion, and the like, but not limited to that. Specific examples of a preferred transition metal salt are cobalt 2-ethylexanoate, cobalt neodecanoate and cobalt stearate. In addition, the transition metal salt can have a polymeric counter anion and thus can be an ionomer, as is generally referred to.
[00243] The lower limit value of the transition metal salt content is, in terms of metal element equivalent, preferably it is 1 ppm, more preferably 5 ppm, and even more preferably 10 ppm with respect to the resin composition. On the other hand, the upper limit value of the transition metal salt content is preferably 50,000 ppm, more preferably 10,000 ppm, and even more preferably 5,000 ppm. The content of the transition metal salt is less than the lower limit described above, the oxygen clearance receptor effect of the obtained multilayer structure may be insufficient. On the other hand, when the content of the transition metal salt is beyond the upper limit described above, the thermal stability of the resin composition is deteriorated, in this way the generation of decomposed gas, and gel and / or seed can be significantly developed. Desiccant [00244] Another component contained in the resin composition that constitutes layer A and layer B is exemplified by a desiccant.
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94/158
The desiccant can be particularly appropriately used also when the resin composition that constitutes layer M contains the adhesive resin. The desiccant can be contained in one of the resin compositions that make up layer A or layer B, it is preferably contained in the composition of layer A resin.
[00245] The desiccant is a substance that absorbs moisture and is capable of removing moisture from a given environment. The desiccant that can be contained in the resin composition of the multilayer structure is not particularly limited as long as it has these properties. Containing the desiccant in the resin layer composition, the gas barrier properties of the resin layer containing the gas barrier resin can be maintained at a high level as long as a dry state is maintained.
[00246] Examples of suitable desiccant include hydrate-forming salts, that is, salts that absorb moisture in the form of crystallization water, in particular phosphoric acid salts and particularly anhydrides thereof, for example, salts such as sodium borate and sodium sulfate, and particularly anhydrides thereof. Alternatively, other moisture-absorbing compounds such as, for example, sodium chloride, sodium nitrate, sugar, silica gel, bentonite, molecular sieve, a high water-absorbing resin or the like can also be used. These can be used alone or a plurality of types thereof.
[00247] The desiccant is preferably dispersed as fine particles in a matrix of the resin layer including the gas barrier resin. In particular, it is advantageous that an average volume surface diameter of the particles having a longitudinal diameter of not less than 10 pm of the desiccant particles is not more than 30 pm, suitably 25 pm, and more appropriately not more than 20 pm, thereby a multilayer structure
Petition 870190056670, of 06/19/2019, p. 98/172
95/158 having a high level of gas barrier properties that have not been achieved so far can be obtained having a finely dispersed formed state. The composition showing such a finely dispersed state can be achieved, provided that special processing methods to meet needs are carefully combined.
[00248] The proportion of the gas barrier resin constituting the resin layer for the desiccant used is not particularly limited, and the mass ratio is preferably in the range of 97: 3 to 50:50, and particularly 95: 5 to 70:30.
[00249] In connection with the desiccant particles in the resin composition that constitutes the resin layer, the average diameter of the particle volume surface, having a longitudinal diameter of not less than 10 pm, has a great influence on the properties of the gas barrier of the multilayer structure that includes the composition of the resin in its layer (s). Although the reason for this phenomenon is not necessarily clarified, it is assumed that particles having a large particle size have particularly disadvantageous effects on the moisture absorption effects or on the gas barrier properties of the gas barrier resin.
[00250] Of the desiccants described above, phosphoric acid salts that can form a hydrate are particularly preferred. Since many phosphoric acid salts can form a hydrate containing a plurality of water molecules in the form of water crystals, the mass of water absorbed per unit mass is large, thus able to significantly contribute to improving barrier properties. gas of the multilayer structure. In addition, since the number of crystallization water molecules capable of including the phosphoric acid salt is likely to increase step by step as the humidity rises, the humidity can be gradual
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96/158 absorbed according to the variation of humidity in the environment. [00251] Illustrative examples of the phosphoric acid salt include sodium phosphate (Na Powder), trilithium phosphate (Li Po), disodium hydrogen phosphate (Na HPO), sodium hydrogen phosphate (NaH PO), polysodium phosphate, lithium phosphate , dilithium hydrogen phosphate, lithium hydrogen phosphate, lithium polyphosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium hydrogen phosphate, disodium hydrogen phosphate, potassium polyphosphate, calcium (Ca (PO)) phosphate, hydrogen phosphate, Ca (PO), hydrogen calcium hydrogen phosphate (Ca (H PO)), polycalcium phosphate, ammonium phosphate, diamonium hydrogen phosphate, polyammonium phosphate and the like. The polyphosphate as referred to herein includes diphosphate (pyrophosphoric acid salts), triphosphate (tripolyphosphoric acid salts) and the like. Of these phosphoric acid salts, anhydrides containing no water of crystallization are appropriate. In addition, sodium phosphate, disodium hydrogen phosphate, and sodium hydrogen phosphate are appropriate.
[00252] Phosphoric acid salts are usually in powder form. Commercially available powders of phosphoric acid salts generally have an average particle diameter of 15 to 25 pm, and the maximum particle size included is 40 to 100 pm. If a powder including large particles is used, the gas barrier properties of the resin layer of the multilayer structure may be insufficient. When particles larger than the thickness of the resin layer of the multilayer structure, gas barrier properties can be significantly compromised. In this way, the particle size of the phosphoric acid salt powder is preferably not greater than the thickness of the resin layer of the multilayer structure.
[00253] In other words, the phosphoric acid salt powder preferably has an average particle diameter of not more than 10
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97/158 pm. The average particle diameter is more preferably not more than 1 pm. The average particle diameter can be determined, for example, by a light scattering method or the like using a particle size analyzer.
[00254] When the phosphoric acid salt is used as a desiccant, it is preferably mixed together with a dispersant. When such a dispersant is mixed, the phosphoric acid salt as a desiccant can be favorably dispersed in the resin composition containing a gas barrier resin. Examples of dispersants include fatty acid salts, glycerin fatty acid esters, fatty acid amides, and the like. It should be noted that glycerin esters of aromatic carboxylic acids are generally in the form of a liquid at room temperature, and are therefore not suitable for dry blending with a phosphoric acid salt.
[00255] The fatty acid salt is exemplified by calcium stearate, zinc stearate, magnesium stearate, and the like. The glycerin fatty acid ester is exemplified by the glycerine monostearic acid ester, octanoyl glyceride monodecanol, and the like. The fatty acid amide is exemplified by the ethylene biosearic acid amide, and the like.
[00256] Of these dispersants, a fatty acid salt is appropriately used in light of improving the sliding properties of phosphoric acid salt powder, and preventing clogging of an extruder screen during melting kneading. Of these, a calcium salt, a zinc salt, and the like are appropriate. In addition, in light of the particularly favorable dispersibility realization, a glycerin fatty acid ester is appropriately used. In particular, a glycerin mono- or digrax acid ester is preferred, monograxic acid ester is more preferred, and glycerin monostearic acid ester is particularly preferred.
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98/158 [00257] Furthermore, the dispersant preferably consists of a compound having 9 to 40 carbon atoms. Due to the number of carbon atoms included in this range, favorable dispersibility can be achieved. The lowest limit value for the number of appropriate carbon atoms is 12, and the upper limit value for the number of appropriate carbon atoms is 30.
[00258] The amount of dispersants mixed is 1 to 20 parts by weight compared to 100 parts by weight of phosphoric acid salt. When the dispersant content is less than 1 part by weight relative to 100 parts by weight of phosphoric acid salt, preventing generation of aggregates of the phosphoric acid salt fails. The dispersant content is suitably not less than 2 parts by weight, and more appropriately not less than 3 parts by weight. On the other hand, when the dispersant content is greater than 20 parts by weight with respect to 100 parts by weight of the phosphoric acid salt, the slip of the pellet of the resin composition becomes so great as to result in difficulty in feeding the extruder, in this way the adhesive strength between layers is impaired to produce the multilayer structure. The content of the dispersant is suitably not more than 15 parts by weight, and more appropriately not more than 10 parts by weight.
Relationship Between Layer A and Layer B [00259] In the multilayer structure, the strength of the adhesive layers between layer A and layer B that are adjacent to each other may be not less than 450 g / 15 mm, preferably not less than 500 g / 15 mm, more preferably not less than 600 g / 15 mm, and even more preferably not less than 700 g / 15 mm, and particularly preferably not less than 700 g / 15. . When the adhesive strength between layers between layer A and layer B falls within the range described above, very favorable adhesion can be provided,
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99/158 in this way superior features of the multilayer structure such as gas barrier properties can still be maintained against deformation such as elongation or bending, and in this way much superior durability can be achieved. In this regard, the interlayer adhesive strength between layer A and layer B, as referred to herein, means a value (unit: g / 15 mm) of peeling resistance T- between layer A and layer B, as determined with a measuring sample having a width of 15 mm using an autograph in an atmosphere of 23 ° C and 50% RH under a condition involving a stress rate of 250 mm / min.
[00260] Regarding the relationship between multilayer structure, it is desired that a bonding reaction is allowed to occur actively at the interface between layer A and layer B. Making a bond forming a reaction between the gas barrier resin in the resin composition of layer A and the thermoplastic resin in the layer B resin composition due to the metal salt included as described above, more superior interlayer adhesion can be realized. The exemplary bonding reaction includes: a hydroxyl group exchange reaction that occurs between a TPU carbamate group, a polyamide amino group or the like with a hydroxyl or similar group of the gas barrier resin; a reaction of adding a hydroxyl or similar group of the gas barrier resin to the isocyanate group remaining in the TPU; an amide producing a reaction of a polyamide terminal carboxyl group with a hydroxyl group of EVOH; as well as another bonding reaction that occurs between the gas barrier resin and the adhesive resin, and the like. As a result, the gas barrier, durability and similar properties of the multilayer structure can be further improved.
[00261] Regarding the viscosity relationship of each resin composition that constitutes layer A and layer B, when
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100/158 the gas barrier resin included in the layer A resin composition is EVOH, or particularly when the Vicat softening temperature of the layer A resin composition is less than 180 ° C, the lower limit of the ratio ( | 2b / | 2a) from the melt viscosity (H2b) of the layer B resin composition to the melt viscosity (Q2a) of the layer A resin composition as determined at a temperature of 210 ° C and a shear rate of 1,000 / s is preferably 0.3, more preferably 0.4, and even more preferably 0.5. On the other hand, the upper limit of the ratio (| 2b / | 2a) is preferably 2, more preferably 1.5, and even more preferably 1.3. When the proportion (| 2b / | 2a) of the viscosity is included in the range described above, the appearance of the multilayer structure becomes favorable in the formation by a multilayer coextrusion process, and the adhesion between layer A and layer B becomes this way, the durability of the multilayer structure can be improved.
[00262] When the gas barrier resin included in the layer A resin composition is a resin that is not the EVOH resin, and particularly when the Vicat softening temperature of the layer A resin composition is not less than 180 ° C , the lower limit of the ratio (γ ^ β '/ γ ^ α) of the melting viscosity (| 2b') of the layer B resin composition to the melting viscosity (| 2a ') of the layer A resin composition, as determined at a temperature higher than the Vicat softening temperature of the layer A resin composition by 30 ° C and at a shear rate of 1,000 / s is preferably 0.3, more preferably 0.4, and even more preferably 0.5. On the other hand, the upper limit of the ratio (Π2β '/ | 2α') from layer B to layer A is preferably 3, more preferably 2, and even more preferably 1.5, and particularly preferable 1.3. When the viscosity ratio (| 2b '/ | 2a') is included
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101/158 in the range described above, the appearance of the multilayer structure becomes favorable in the formation by a multilayer coextrusion process, and the adhesion between layer A and layer B becomes favorable, in this way the durability of the multilayer structure can be enhanced.
[00263] In addition, when the resin has a high melting point, the lower limit of the ratio (η '' / η '') of the melting viscosity (η '') of the layer A resin composition as determined at a a temperature of 220 ° C and a shear rate of 1,000 / s is preferably 0.5, more preferably 0.6, and even more preferably 0.7. On the other hand, the upper limit of the ratio (η '' / η '') of the melt viscosity of layer A and layer B is preferably 2, more preferably 1.5, and even more preferable 1.3. When the viscosity ratio is included in the range described above, the appearance of the multilayer structure becomes favorable to form a multilayer coextrusion process, and the adhesion between layer A and layer B becomes favorable, thus the durability of the structure multilayer can be improved.
Method for Producing Multilayer Structure [00264] The method for producing multilayer structure is not particularly limited until the method can favorably laminate and adhere layer A and layer B, and any of the well known methods such as, for example, coextrusion, stick together , coating, bonding, and coupling can be employed. The method for producing multilayer structure is specifically exemplified by (1) a method for producing multilayer structure having a layer A and a layer B through a multilayer coextrusion process using a resin composition for layer A containing a barrier resin. gas such as EVOH, and a resin composition for layer B containing a thermoplastic resin, (2) a method
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102/158 to produce multilayer structure having a layer A and a layer B, the method including: first producing a laminate including a layer that will be layer A and a layer that will be layer B by a coextrusion process using a resin composition for layer A containing a gas barrier resin such as EVOH and a resin composition for layer B containing a thermoplastic resin; (2) a method for producing multilayer structure having a layer A and a layer B, the method including: producing a first laminate including a layer that will be layer A and a layer that will be layer B by a co-extrusion process using a resin composition for layer A containing a gas barrier resin such as EVOH and a resin composition for layer B containing thermoplastic resin: coating a plurality of laminates through an adhesive; and lengthening, and the like. Among these, superior productivity light, excellent adhesion between layers, (1) the method of forming by a multilayer co-extrusion process using a resin composition containing a gas barrier resin like EVOH and a resin composition containing thermoplastic resin is preferred.
[00265] In the multilayer coextrusion process, the multilayer structure is formed by: heating melting the layer A resin composition to layer B resin composition; supply a composition of resin cast in a matrix extrusion of each distinct extruder and pump through each channel; extrude from the extrusion die to give a multilayer; and after that leave for lamination and adhesion. As the extrusion die, for example, a multi-distribution die, a field block, a static mixer or similar, can be used.
Applications [00266] The multilayer structure is also superior in capacity. Petition 870190056670, of 19/06/2019, p. 106/172
103/158 cross-layer adhesion, as described above, and has superior gas barrier properties, elongation, thermoformability and durability. In this way, the multilayer structure can be used for food packaging materials, medical bottle packaging materials, industrial plate materials, etc., plate materials for architectural materials and agricultural plate materials, and other plate materials , as well as several other types of pipes, and the like.
[00267] Examples of food packaging material that is an application for use in food packaging include bags for food or confectionery packaging (flexible packaging), wrapping films for food, films for peel packaging, stretch films, wrapping films. shrinkage, sterilization bottles, and the like. Since food packaging materials having a multilayer structure have superior gas barrier properties, elongation capacity, thermoformability and durability, long-term storage and sterilization resistance can be improved, and thus such sterilization bottles can be improved. used as an alternative to metal canisters.
[00268] Examples of other bottle packaging materials include various types of bottle packaging materials for cosmetics, industrial chemicals, fertilizer pesticides, cleansers, etc., shopping bags, garbage bags, fertilizer bags, bag-in-boxes , flexible tanks and the like.
[00269] The bag-in-boxes means a bottle in which the thin-walled foldable inner bottle is combined with an outer box such as a cardboard box showing storage capacity, portability, protective properties for inner bottle, stamping, and the like. The base material of the outer box can be a
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104/158 cardboard, or instead plastic or metal. The shape of the outer box can be and can be not only a box shape, but also a cylindrical shape, etc. For the inner bag-in-box vial, the multilayer structure of the present invention can be used appropriately. The bag-in-box can be used to transport, store, display, etc., food such as wine, juice, mirim (kitchen sauces - Japanese cuisine), soy sauce, sauce, noodle sauce, milk, mineral water , Japanese sauce, shocu (distilled extract), coffee and tea, and various types of cooking oils as well as non-foods such as liquid fertilizers, developmental solutions, battery solution and other industrial chemicals, and the like. [00270] Flexible tank means a flask formed of a base material showing flexibility, and can be one provided with a frame to support the flask, or one without having a frame and being able to maintain its shape through the resulting pressure of gas , liquid, etc., stored in the bottle. The flexible tank can be stored in a compact way in a folded form during the unused period of time, while when it is to be used, assembly or expansion allows use as a tank. When the multilayer structure of the present invention is used as a flexible tank base material, durability and gas barrier properties of the flexible tank can be improved.
[00271] Examples of industrial sheet materials, etc., include films for sealing devices, gas collection films, bio-reactors and the like.
[00272] The film for sealing material devices can be appropriately used for each application for which superior adhesiveness, gas barrier properties, durability and the like are required as back plates for solar cells.
[00273] The gas collection film is exemplified by films of
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105/158 hydrogen barrier laminated on the inner face, etc., of collection bags to analyze exhaust gas, bags collecting hydrogen in hydrogen stations of fuel cell vehicles, high pressure hydrogen bottles of fuel cell vehicles , and the like.
[00274] The router as referred to means a device to perform a biochemical reaction using a biocatalyst. The multilayer structure of the present invention can be appropriately used for a reactor chamber, a pipe and the like of the bioreactor. By using the multilayer structure in a bioreactor, gas barrier properties, durability and the like of the bioreactor can be improved, and superior thermoformability can also be achieved.
[00275] Examples of sheet material for architectural materials include vacuum thermal insulation boards, wallpapers and the like. The vacuum insulation board provided with the multilayer structure of the present invention has superior gas barrier properties, and thus superior vacuum holding capacity can be displayed. In addition, since wallpapers provided with the multilayer structure of the present invention have improved elongation and thermoformability, productivity and feasibility can be improved, and due to the excellent durability, use over a long period of time is possible.
[00276] Examples of agricultural plate materials include multi-films for fumigation, greenhouse films, and the like. When the multilayer structure of the present invention is used, for example, multi-films for agricultural fumigation, fumigation can be efficiently performed due to the superior gas barrier properties, and the film is less likely to break due to the superior durability, in this way practicality is improved.
[00277] Like the other sheet material, for example, the use of ge
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106/158 omembranes, random barrier films, and the like are exemplified. The geomembrane is a plate used as infiltration control work for waste disposal plants, and the like. The random barrier film prevents the diffusion of gaseous radon generated by uranium decomposition in waste disposal plants. Since the multilayer structure of the present invention is superior in gas barrier properties, durability and the like as described above, it can be appropriately used for these applications.
[00278] The multilayer structure of the present invention is suitably applied to food packaging materials that particularly require superior gas barrier properties, elongation, durability, transparency and the like, between each of the applications. It should also be noted that the classification of each application has been made on the basis of general use, and each product is not limited to the applications of each field. For example, vacuum thermal insulation boards can be used not only as a sheet material for architectural materials, but also as an industrial sheet material, and the like.
[00279] The multilayer structure of the present invention is not limited to the previous embodiments. For example, another layer may be included in addition to layer A and layer B. The type of resin composition that may constitute other layers is not particularly limited, but preferably has strong adhesion to layer A and / or layer B. As another layer, one having a hydroxyl or similar group included in the gas barrier resin in layer A, or having a molecular chain including a functional group that generates a bond through a reaction with a functional group (for example a carbamate group or an isocyanate group in the molecular chain of TPU) in layer B, is particularly preferablePetition 870190056670, of 19/06/2019, p. 110/172
107/158 da.
[00280] In addition, the multilayer structure of the present invention can have a laminated support layer on one or both sides of the laminate mentioned above having not less than 8 layers of resin. The backing layer is not particularly limited, and may not be a resin layer, and, for example, a general synthetic resin layer, a synthetic resin film or the like can be used. In addition, lamination medium of the backing layer is not particularly limited, and adhesion by an adhesive, extrusion lamination, or the like can be employed.
EXAMPLES [00281] Hereinafter, the present invention is explained in a more specific way by way of Examples, but the present invention is not limited to the following Examples.
(Production example 1: Pellet example (A-1)) [00282] In a polymerization tank equipped with a cooling device and a mechanical stirrer, 20,000 parts by weight of vinyl acetate, 2,000 parts by weight of methanol, 10 parts by mass of 2,2'-azobis- (4-methoxy-2,4dimethylvaleronitrile) as a polymerization initiator, and the nitrogen substitution was performed while stirring. Thereafter, ethylene was introduced for this purpose, followed by adjusting the internal temperature to 60 ° C and the ethylene pressure to 45 kg / cm ² , and the temperature and pressure were maintained for 4 hours while stirring to allow polymerization. Then, sorbic acid (SA) in an amount of 10 parts by weight (0.05% by weight compared to loaded vinyl acetate) was dissolved in methanol to prepare a 1.5% by weight solution, which was added to the polymerization tank. The degree of polymerization was 45% in relation to the loaded vinyl acetate. The copolymerization reaction liquid was supplied for coPetition 870190056670, of 06/19/2019, p. 111/172
108/158 purging luna, and then unreacted vinyl acetate was removed from the top of the tower by introducing methanol vapor from the bottom of the tower, a 40% methanol solution of the copolymer was obtained. The copolymer had an ethylene unit content of 32.5 mol%, and a vinyl acetate unit content of 67.5 mol%.
[00283] A methanol solution of the copolymer was introduced into a saponification reaction flask, and then a sodium hydroxide / methanol solution (85 g / L) was added in order to reach 0.5 equivalent with respect to the component of vinyl acetate in the copolymer. After that, methanol was added to adjust the copolymer concentration to 15 wt%. The temperature in the reaction flask was raised to 60 ° C, and the reaction was left while blowing nitrogen gas into the reaction flask for 5 hours. After that, the reaction was stopped by neutralizing with acetic acid, and the content was removed from the reaction flask and left for deposition in a particular form by leaving it standing at ordinary temperature. An operation including sliding particles deposited with a centrifugal separator and adding a large amount of water followed by repeated sliding to obtain EVOH (A-1) with a saponification degree of 99.5% (density: 1.19 g / cm ³ ).
[00284] EVOH (A-1) thus obtained was subjected to a treatment with an aqueous solution containing acetic acid, sodium acetate, sodium hydrogen phosphate and ortho-boric acid (OBA) (an aqueous solution containing 0.3 g of acetic acid , 0.2 g of sodium acetate, 0.05 g of sodium hydrogen phosphate and 0.35 g of orthoboric acid dissolved in 1 L), in a 20 bath ratio, followed by drying and pelleting with an extruder to give a pellet (A-1). The MFR of the pellet (A-1) was 1.8 g / 10 min (190 ° C, under a load of 2160 g). In addition, the pellet (A-1) had an acetate content of 150 ppm, a
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109/158 sodium ion content of 140 ppm, a content of the phosphate compound in terms of phosphoric acid group equivalent of 45 ppm, and a content of boron compound in terms of an equivalent boron value of 260 ppm.
(Production Example 2: Pellet Example (A-2)) [00285] In a polymerization tank equipped with a cooling device and a stirrer, 20,000 parts by mass of vinyl acetate, 4,000 parts by weight of methanol, were loaded, 10 parts by weight of acetyl peroxide as a polymerization initiator (500 ppm with respect to the amount of vinyl acetate loaded), 0.4 parts by weight of citric acid (20 ppm with respect to the amount of vinyl acetate loaded), and 560 parts by mass of
3,4-diacetoxy-1-butene, and the substitution with nitrogen was carried out with stirring. After that, ethylene was introduced for this purpose, followed by the adjustment of the internal temperature to 67 ° C and the ethylene pressure to 35 Kg / cm ² . Subsequently, the polymerization was left while gradually adding 3,4-diacetoxy-1-butene in a total amount of 180 parts by mass for 6 hours until the degree of polymerization reached 50% with respect to the loaded vinyl acetate. After that, sorbic acid (SA) in an amount of 10 parts by weight (500 ppm in relation to the amount of vinyl acetate loaded) was dissolved in methanol to prepare a 1.5% by weight solution, which was added to the tank polymerization. The copolymerization reaction liquid was supplied to the purge column, and then unreacted vinyl acetate was eliminated from the top of the tower by introducing methanol vapor from the bottom of the tower, a 40% mass methanol solution copolymer was obtained. The copolymer had an ethylene unit content of 29.0 mol%.
[00286] A methanol solution of the copolymer was introduced into the saponification reaction flask and then a hydroxide solution
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110/158 sodium / methanol (85 g / L) was added in order to reach 0.5 equivalent in relation to the vinyl acetate component in the copolymer. For that purpose, methanol was added to adjust the copolymer concentration to 15% by mass. The temperature in the reaction flask was raised to 60 ° C, and the reaction was left while blowing nitrogen gas into the reaction flask for 5 hours. After that, the reaction was stopped by neutralization with acetic acid, and the content was removed from the reaction flask and left for deposition in a particulate form leaving it at a common temperature. An operation including sliding the deposited particles with a centrifugal separator and adding a large amount of water followed by sliding was repeated to obtain EVOH (A-2) with a saponification degree of 99.5% (density: 1.19 g / cm ³ ). [00287] It should be noted that as the structural unit (I) of EVOH (A-2) instead of the ethylene unit and the vinyl alcohol unit, a structural unit having the following structure was introduced, and the quantity introduced was 2.5 mol% from determination by ¹ H-NMR (substance of internal standard: tetramethylsilane; solvent: d6-DMSO).
- ch ₂ ch -
I
H - C— OH
I
H - C — OH
H [00288] EVOH (A-2) obtained in this way was subjected to a treatment with an aqueous solution containing acetic acid, sodium acetate, spodium hydrogen phosphate and ortho-boric acid (OBA) (an aqueous solution containing 0.3 g of acid acetic acid, 0.2 g sodium acetate, 0.07 g sodium hydrogen phosphate and 0.32 g ortho-boric acid
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111/158 dissolved in 1 L), in a 20 bath ratio, followed by drying and pelletizing with an extruder to give a pellet (A-2). The MFR of the pellet (A-2) was 1.2 g / 10 min (190 ° C, under a load of 2160 g). In addition, the pellet (A-2) had an acetate content of 150 ppm, a sodium content of 150 ppm, a content of the phosphate compound in terms of phosphoric acid group equivalent of 50 ppm, and a content of the compound boron in terms of an equivalent boron value of 150 ppm.
(Production Example 3: Pellet Example (A-3)) [00289] In a polymerization tank equipped with a cooling device and a stirrer, 20,000 parts by mass of vinyl acetate, 1,020 parts by weight of methanol were loaded ,
3.5 parts by mass of 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile) as a polymerization initiator, and the substitution with nitrogen was carried out while stirring. Thereafter, ethylene was introduced for this purpose, followed by adjusting the internal temperature to 60 ° C and the ethylene pressure to 59 kg / cm ² , and the temperature and pressure were maintained for 4 hours while stirring to allow polymerization. Then, sorbic acid (SA) in an amount of 10 parts by weight (0.05% by weight with respect to loaded vinyl acetate) was dissolved in methanol to prepare a 1.5% by weight solution, which was added to the polymerization tank. The degree of polymerization was 30% with respect to the loaded vinyl acetate. The copolymerization reaction liquid was supplied to the purge column, and after the unreacted vinyl acetate was removed from the top of the tower by the introduction of methanol vapor from the bottom of the tower, a 40% mass methanol solution copolymer was obtained. The copolymer had an ethylene unit content of 44.5 mol%, and a vinyl acetate unit content of 55.5 mol%.
[00290] A methanol solution of the copolymer was introduced into
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112/158 a saponification reaction vial, and then a sodium hydroxide / methanol solution (85 g / L) was added in order to reach 0.5 equivalent with respect to the vinyl acetate component in the copolymer. To that end, methanol was added to adjust the copolymer concentration to 15% by mass. The temperature in the reaction flask was raised to 60 ° C, and the reaction was left while insufflating nitrogen gas in the reaction flask for 5 hours. After that, the reaction was stopped by neutralization with acetic acid, and the content was removed from the reaction flask and left for deposition in a particulate form, leaving the common temperature. An operation including sliding particles deposited with a centrifugal separator and adding a large amount of water followed by repeated sliding to obtain EVOH with a saponification degree of 99.5%.
[00291] EVOH thus obtained was subjected to a treatment with an aqueous solution containing acetic acid and sodium hydrogen phosphate (an aqueous solution containing 0.05 g of acetic acid, 0.02 g of sodium hydrogen phosphate and 0.03 g of orthoboric acid dissolved in 1 L) in a 20 bath ratio, followed by drying to give particles of the EVOH composition. As the particles of the EVOH composition had MFR of 4.6 g / 10 min (190 ° C, under a load of 2160 g). In addition, the particles of the EVOH composition had an acetate content of 40 ppm, a phosphate compound content in terms of equivalent phosphoric acid group of 20 ppm.
[00292] Using the particles of the EVOH composition obtained as described above, epoxypropane was allowed to react with EVOH by means of a biaxial extruder TEM-35BS (37 mmç, L / D = 52.5) manufactured by Toshiba Machine Co., Ltd. Under the conditions of extrusion as follows while adding a catalyst. Unreacted epoxypropane was eliminated from a vent, and then 8.2% by weight.
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113/158 sa of aqueous ethylenediamine trisodium hydrate solution was added as a catalyst extinguisher to allow pelletizing, followed by drying to give a pellet (A-3) that includes EVOH-modified ethylene-vinyl alcohol copolymer (A-3) presenting the following structure (density: 1.13 g / cm ³ ) as a structural unit (II) instead of the ethylene unit and the vinyl alcohol unit.
- CH2CH -
I o
I CH ₃ —c — H
I
H - C - H
I OH [00293] Cylinder, die temperature assemblies:
[00294] Resin feed port / inlet part of the cylinder / adapter matrix / matrix = 160/200/240/240 (° C)
Thread rotation speed: 400 rpm [00295] Feed rate of ethylene vinyl alcohol copolymer: 16 kg / hr [00296] Feed rate of epoxypropane: 2.4 kg / hour (pressure during feeding: 6 MPa) [00297 ] Feed rate of catalyst solution: 0.32 kg / hour [00298] Catalyst preparation: Zinc acetylacetonate monohydrate in an amount of 28 parts by mass was mixed with 957 parts by mass of 1,2-dimethoxyethane to give a mixed solution. In order to result in a mixed solution, 15 parts by mass of trifluoromethane sulfonic acid were added
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114/158 while stirring, in this way a catalyst solution was obtained. In other words, 1 mole of trifluoro methane sufonic acid was added to 1 mole of zinc acetylacetonate monohydrate to prepare a mixed solution.
[00299] Feed rate of aqueous catalyst extinguisher solution: 0.16 kg / hr [00300] MFR of the resulting pellet (A-3) was 3.2 g / 10 min (190 ° C, under a load of 2160 g). In addition, the pellet (A-3) had an acetate content of 420 ppm, a zinc ion content of 120 ppm, a sodium content of 130 ppm, a content of the phosphate compound in terms of phosphoric acid equivalent 20 ppm, a trifluoromethane sulfonic acid ion content of 280 ppm, and a boron compound content in terms of a boron equivalent value of 12 ppm. In addition, the amount of the structural unit (II) instead of ethylene undiade and the EVOH vinyl alcohol unit (A-3) introduced (amount of epoxybutane modification) was, as determined by ¹ H-NMR (substance of internal standard: tetramethylsilane; solvent: d6-DMSO) was 5.8 mol%.
(Production Example 4: Pellet Example (A-4)) [00301] A pellet (A-4) was obtained in a similar manner to Production Example 1 except that EVOH (A-1) having a units of ethylene of 32.5% by mol and a degree of saponification of 99.5% was subjected to a treatment using an aqueous solution containing acetic acid, sodium acetate, sodium hydrogen phosphate and orthoboric acid (OBA) (aqueous solution containing 0.3 g of acetic acid, 0.4 g of sodium acetate, 0.10 g of sodium hydrogen phosphate and 0.70 g of orthoboric acid dissolved in 1 L) in a bath ratio of 20 in Production Example 1 The pellet MFR (A-
4) was 1.0 g / 10 min (190 ° C, under a load of 2160 g). In addition, the pellet (A-4) had an acetate content of 210 ppm, an ion content of
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115/158 sodium of 280 ppm, a content of the phosphate compound in terms of the equivalent phosphoric acid group of 90 ppm, and a content of the boron compound in terms of an equivalent boron value of 520 ppm. (Production Example 5: Pellet Example (A-5)) [00302] A pellet (A-5) was obtained in a similar manner to Production Example 1 except that EVOH (A-1) having a unit content of ethylene of 32.5% by mol and a degree of saponification of 99.5% was subjected to a treatment using an aqueous solution containing acetic acid, sodium acetate, sodium hydrogen phosphate and orthoboric acid (OBA) (aqueous solution containing 0 , 3 g of acetic acid, 0.02 g of sodium acetate, 0.005 g of sodium hydrogen phosphate and 0.35 g of orthoboric acid dissolved in 1 L) in a 20 bath ratio in Production Example 1. The MFR of the pellet (A-5) was 1.6 g / 10 min (190 ° C, under a load of 2160 g). In addition, the pellet (A-5) had an acetate content of 95 ppm, a sodium ion content of 14 ppm, a content of the phosphate compound in terms of the phosphoric acid group equivalent of 5 ppm, and a boron compound content in terms of a boron equivalent value of 260 ppm.
(Production Example 6: Pellet Example (A-6)) [00303] A pellet (A-6) was obtained in a similar way to Production Example 1 except that EVOH (A-1), presenting the content of units of ethylene of 32.5% by mol and a degree of saponification of 99.5%, was subjected to a treatment using an aqueous solution containing acetic acid, sodium acetate, sodium hydrogen phosphate and orthoboric acid (OBA) (aqueous solution containing 0.3 g of acetic acid, 2.0 g of sodium acetate, 0.1 g of sodium hydrogen phosphate and 0.35 g of orthoboric acid dissolved in 1 L) in a bath ratio of 20 in the Production Example 1. The MFR of the pellet (A6) was 2.5 g / 10 min (190 ° C, under a load of 2160 g). In addition, the pellet (A-6) had an acetate content of 680 ppm, an ion content of
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116/158 sodium of 1,170 ppm, a content of the phosphate compound in terms of the phosphoric acid group equivalent of 90 ppm, and a content of the boron compound in terms of an equivalent boron value of 250 ppm. (Production Example 7: Pellet Example (A-7)) [00304] A pellet (A-7) was obtained in a similar way to Production Example 1 except that EVOH (A-1), having a content of units of ethylene of 32.5% by mol and a degree of saponification of 99.5%, was subjected to a treatment using an aqueous solution containing acetic acid, magnesium acetate, sodium hydrogen phosphate and orthoboric acid (OBA) (aqueous solution containing 0.3 g of acetic acid, 0.2 g of magnesium acetate, 0.05 g of sodium hydrogen phosphate and 0.35 g of orthoboric acid dissolved in 1 L) in a bath ratio of 20 in Production Example 1. The MFR of the pellet (A-7) was 2.8 g / 10 min (190 ° C, under a load of 2160 g). In addition, the pellet (A-7) had an acetate content of 150 ppm, a sodium ion content of 25 ppm, a magnesium ion content of 110 ppm, a content of the phosphate compound in terms of the equivalent of phosphoric acid group of 45 ppm, a boron compound content in terms of a boron equivalent value of 260 ppm.
(Production Example 8: Pellet Example (A-8)) [00305] A pellet (A-8) was obtained in a similar way to Production Example 1 except that EVOH (A-1), presenting the content of ethylene units of 32.5% by mol and a degree of saponification of 99.5%, was subjected to a treatment using an aqueous solution containing acetic acid, phosphoric acid and orthoboric acid (OBA) (aqueous solution containing 0.3 g of acetic acid, 0.06 g of phosphoric acid and 0.35 g of orthoboric acid dissolved in 1 L) in a bath ratio of 20 in Production Example 1. The pellet MFR (A-8) was 1, 6 g / 10 min (190 ° C, under a load of 2160 g). In addition, the pellet (A-8) had an acetate content of 90 ppm, a content of
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117/158 phosphate compound in terms of the equivalent of the 43 ppm phosphoric acid group, and a boron compound content in terms of a boron equivalent value of 260 ppm.
(Production Example 9: Pellet Example (A-9)) [00306] A pellet (A-9) was obtained in a similar way to Production Example 1 except that EVOH (A-1) having a unit content of ethylene of 32.5% by mol and a degree of saponification of 99.5% was subjected to a treatment using an aqueous solution containing acetic acid, sodium acetate, sodium hydrogen phosphate and orthoboric acid (OBA) (aqueous solution containing 0 , 3 g of acetic acid, 40.0 g of sodium acetate, 0.1 g of sodium hydrogen phosphate and 0.35 g of orthoboric acid dissolved in 1 L) in a bath ratio of 20 in Production Example 1. The pellet MFR (A-
9) was 6.8 g / 10 min (190 ° C, under a load of 2160 g). In addition, the pellet (A-9) had an acetate content of 13,500 ppm, a sodium ion content of 23,000 ppm, a content of the phosphate compound in terms of the phosphoric acid group equivalent of 90 ppm, and a boron compound content in terms of a boron equivalent value of 250 ppm. (Production Example 10: Pellet Example (A-10)) [00307] A pellet (A-10) was obtained in a similar way to Production Example 1 except that EVOH (A-1) having a unit content of ethylene of 32.5% by mol and a degree of saponification of 99.5% was subjected to a treatment using an aqueous solution containing acetic acid, sodium acetate, sodium hydrogen phosphate and orthoboric acid (OBA) (aqueous solution containing 0.3 g of acetic acid, 0.2 g of sodium acetate, 0.05 g of sodium hydrogen phosphate and 7.0 g of orthoboric acid dissolved in 1 L) in a bath ratio of 20 in Production Example 1 The pellet MFR (A-
10) was 0.05 g / 10 min (190 ° C, under a load of 2160 g). In addition, the pellet (A-10) had an acetate content of 150 ppm, an ion content of
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118/158 sodium of 140 ppm, a content of the phosphate compound in terms of the equivalent of the phosphoric acid group of 45 ppm, and a content of the boron compound in terms of an equivalent boron value of 5,000 ppm.
(Production Example 11: Pellet Example (A-11)) [00308] In a reaction chamber equipped with a stirrer and a partial condenser, 600 parts by mass of purified adipic acid were added, and heated under a nitrogen vapor to merge the content. Thereafter, when heated to 180 ° C, 560 parts by mass of m-xylylene diamine having a purity of 99.93% by mass were added in drops under normal pressure while still raising the temperature. When the internal temperature reached 250 ° C, the dropwise addition of m-xylylene diamine was ceased, and the mixture was further stirred under normal pressure for an additional hour, after the internal temperature had reached 255 ° C. Thereafter, the reaction product was recovered, and then sprayed after cooling in air to obtain particulate poly-m-xylylene adipamide. The particulate material obtained in this way was loaded into a solid-phase vacuum laminating apparatus, and an operation including reducing the pressure to not more than 200 Pa, while rotating at 10 rpm, and rising to normal pressure with not less than 99 % by volume nitrogen was repeated three times. Thereafter, the internal temperature of the solid phase polymerization apparatus was raised from room temperature to 220 ° C at a temperature rise rate of 50 ° C / hour to conduct the solid phase polymerization by heating the particulate matter. Specifically, in solid phase polymerization, the vacuum operation was started when the temperature of the particulate matter reached 135 ° C, and the cooling was started 360 min after the temperature of the particulate matter reached 150 ° C under normal nitrogen pressure. After that, when the temperature of the matter
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119/158 particulate became no more than 80 ° C under nitrogen vapor, fine powder coupled on the surface of the particulate matter was eliminated to coordinate the size of the particulate matter to 6 to 10 meshes. After the resulting particulate matter was subjected to melt extrusion using a biaxial extruder at 260 ° C to give a bead, pelletization was performed to obtain an MXD6 nylon pellet (density: 1.22 g / cm ³ ). The resulting pellet (A-11) had a Vicat softening temperature of 225 ° C.
[00309] The pellet (A-11) had a melting viscosity η ^ 'of 1,100 Pa-s, er ^ A of 230 Pa ^ s, as determined at a temperature (255 ° C) that is higher than that Vicat softening temperature by 30 ° C, and thus (1/2) logw (^ '/ qZ) was -0.340. (Production Example 12: Pellet Example (A-12)) [00310] Glycolic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was loaded into an autoclave reaction flask, and the temperature was raised to 200 ° C by heating for about 2 hours while stirring to allow condensation while the water generated was distilled. Subsequently, a low boiling point fraction was distilled by reducing the pressure to 20 kPa and maintaining it for 2 hours to prepare a glycolic acid oligomer. The glycolic acid oligomer, in an amount of 120 parts by mass, was loaded into a reaction chamber, and for that purpose 500 parts by mass of benzylbutyl phthalate (manufactured by Junsei Chemical Co., Ltd.) were added as a solvent, and 15 parts by weight of polypropylene glycol (manufactured by Junsei Chemical Co., Ltd., # 400) as a solubilizing agent. In a nitrogen gas atmosphere, depolymerization of the glycolic acid oligomer solution phase was allowed by heating the mixture to about 270 ° C under a pressure of 5 kPa, and the glycolide produced in this way was co-distilled with phthalate of benzylbutyl. For co-distillate
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The resulting 120/158 cyclohexane was added in a volume of about 2 times, thereby allowing the glycolide to be precipitated from benzylbutyl phthalate, and the glycolide was filtered. The filtered material was recrystallized from ethyl acetate, and dried under reduced pressure to obtain purified glycolide. The synthetic glycolide in an amount of 100 parts by weight, 0.006 parts by weight of tin octanoate and 0.05 parts by weight of lauryl alcohol were loaded into a reaction chamber, and the polymerization was left at 220 ° C for 3 hours . Following polymerization, the polymer produced was removed after cooling, and sprayed to obtain a particulate polymer. The particulate matter was washed with acetone, dried in vacuo at 30 ° C, and the size of the obtained particulate matter was adjusted. After the resulting particulate matter was subjected to melt extrusion using a biaxial extruder at 240 ° C to give a bead, pelletization was performed to obtain a pellet (A-12) of polyglycolic acid (PGA) (density: 1.60 g / cm ³ ). The resulting pellet (A-12) had a Vicat softening temperature of 204 ° C.
[00311] The pellet (A-12) had a melting viscosity r1A of 850 Pa-s, er | 2A of 210 Pa-s, as determined at a temperature (234 ° C) that is higher than the temperature of Vicat softening by 30 ° C, and in this way (1/2) logw (Γ2α '/ Γ1α') was -0,304. (Production Example 13: Pellet Example (A-13)) [00312] In a reaction flask equipped with a stirrer, a vacuum port and a nitrogen feed port, 108 parts by mass of p-acetoxybenzoic acid were loaded , and 76.8 parts by weight of 0.70 dl / g of polyethylene terephthalate having a limiting viscosity as determined using a mixed solvent of equivalent mass of phenol / tetrachloroethane at 30 ° C. After the air in the reaction system was replaced with nitrogen three times, the mixture was stirred under nitrogen steam at 280 ° C for about 1 hour.
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121/158 hour, in this way acetic acid in an amount of about 90% theoretical amount of distillation was distilled. Subsequently, the system pressure was gradually reduced to allow a reaction at a final pressure of not more than 1 mmHg. When the polymerization reaction was complete, the resulting reaction product was extruded from a nozzle in the form of a cord and colored to give a cylindrical pellet (A-13) of a fully aromatic liquid crystal polyester (density: 1, 45 g / cm ³ ). The resulting pellet (A-13) had a Vicat softening temperature of 193 ° C.
[00313] The pellet (A-13) had a melting viscosity r1A of 790 Pa-s, er | 2A of 310 Pa ^ s, as determined at a temperature (223 ° C) that is higher than the temperature of Vicat softening by 30 ° C, and thus (1/2) logw (r2A '/ r1A') was -0,203.
(Production Example 14: Pellet Example (B-14)) (Example of Debug Receptor Synthesis: Polyioctonylene Synthesis) [00314] Air in a 5 L three-neck flask equipped with a stirrer and a thermometer has been replaced with dry nitrogen, and thereafter 624 parts by weight of heptane dissolving 110 parts by weight of cis-cyclooctane and 187 parts by weight of cis-4-octane were loaded.
[00315] Then, a catalyst solution was prepared by dissolving 0.0424 parts by mass of [1,3-bi— (2,4,6-trimethylphenyl) -2imidazolidinylidene] dichloro (phenylmethylene) (tricyclohexylphosphine) ruthenium in 3, 00 parts by mass of toluene, and the solution was quickly added to the aforementioned heptene solution to allow a polymerization of ring opening metathesis (ROMP) at 55 ° C. An hour later, an analysis with gas chromatography (prepared by Shimadzu Corporation, GC-14B; Column: prepared by Chemicals Inspection & Testing Institute, Japan, G-100) was conducted to verify
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122/158 disappear cis-cyclooctane. Thereafter, 1.08 parts by mass of ethyl vinyl ester were added, and the mixture was stirred for an additional 10 minutes.
[00316] To the resulting reaction liquid, 600 parts by mass of methanol were added, and the mixture was stirred at 55 ° C for 30 min, followed by allowing to stand at 40 ° C for 1 hour. Then the liquid was separated, and the sublayer (methanol layer) was eliminated. To this was added 600 parts by mass of methanol again, and the mixture was stirred at 55 ° C for 30 min, followed by standing at 40 ° C for 1 hour. After liquid separation was conducted, the sublayer (methanol layer) was eliminated. Heptane in the heptane layer (top layer) was distilled under vacuum, and further dried with a vacuum dryer at 1 Pa and 100 ° C for 6 hours to give 93.7 parts by mass of a polymer (yield: 88%) presenting an average molecular weight (Mw) of 168,000 and an average number of molecular weight (Mn) of 37,000. The proportion of carbon-carbon double bonds in the polymer side chain (polyoctenylene) in relation to carbon-carbon double bonds was 0%.
[00317] The pellet (A1) obtained in Production Example 1 in an amount of 90 parts by weight, 10 parts by weight of polyoctenylene obtained in the Synthesis Example described above, and 0.4242 parts by weight of cobalt (II) stearate ) (0.0400 parts by mass in terms of cobalt atom) were mixed dry, and extruded using a biaxial extruder TEM-35BS (37 mmp, L / D = 52.5) manufactured by Toshiba Machine Co. Ltd. Under conditions extrusion as in the following. After pelletizing, drying gave a pellet (A-14) of a composition containing EVOH (A-1), polyoctenylene and cobalt stearate.
[00318] Cylinder, matrix temperature compositions:
cylinder part / part resin feeding port
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123/158 cylinder / adapter / die = 160/200/220/220 (° C) thread rotation speed: 200 rpm feed rate: 20 kg / hour [00319] MRF of the resulting pellet (A-14) was 4.5 g / 10 min (210 ° C, under a load of 2160 g). In addition, the pellet (A-14) had an acetto content of 105 ppm, a sodium ion content of 125 ppm, a cobalt ion content of 400 ppm, a content of the phosphate compound in terms of acid group phosphoric equivalent of 40 ppm, and a boron compound content in terms of group of equivalent boron value of 230 ppm.
(Production Example 15: Pellet Production (B-1-1a) [00320] A thermoplastic polyurethane resin (TPU) was produced by melting a mixture of: 68.8% by weight of polyesterdiol with 2.0 hydroxyl groups per molecule and having an average number of molecular weight of 1,000, obtained by letting 1,4butanediol react with adipic acid; 27.5 wt% of 4,4-diphenyl methanediisocyanate; and 3.7 wt% of 1,4-butanediol using a multiple screw extruder (matrix temperature: 260 ° C) for 20 min. This thermoplastic polyurethane resin was designated as TPU (B-1) (density: 1.16 g / cm ³ ; hardness of Strut A: 85 The TPU (B-1) obtained in this way was used as a pellet (B-1a).
(Production Example 16: Pellet Example (B-1-1b)) [00321] With 100 parts by weight of TPU (B-1) obtained as described above, 0.37 parts by weight of sodium stearate were mixed melted using a biaxial extruder to produce a pellet (B-1b). The sodium ion content in the pellet (B-1b) was 140 ppm. (Production Example 17: Pellet Example (B-1-2a)) [00322] A thermoplastic polyurethane resin (TPU) was produced by kneading by melting a mixture of: 61.6% by weight of the polyesterdiol described above; 32.3% by mass of 4,4-diphenyl methanodi Petition 870190056670, of 19/06/2019, p. 127/172
124/158 isocyanate; and 6.1% by mass of 1,4-butanediol by means of a multiple screw extruder (matrix temperature: 260 ° C) for 20 min. This thermoplastic polyurethane resin was designed as TPU (B-2) (density: 1.17 g / cm ³ ; Hardness of Strut A: 90). The TPU (B-2) thus obtained was used as a pellet (B-2a).
(Production Example 18: Pellet Example (B-1-2b)) [00323] With 100 parts by weight of TPU (B-2) obtained as described above, 0.27 parts by weight of magnesium stearate were mixed by melting by means of a biaxial extruder to produce a pellet (B-2b). The magnesium ion content in the pellet (B-2b) was 110 ppm. (Production Example 19: Pellet Example (B-1-3a)) [00324] A thermoplastic polyurethane (TPU) resin was produced by melting a mixture of: 60.5% by weight of polytetramethylene glycol having 2.0 hydroxyl groups per molecule and an average molecular weight number of 1,000; 33.1% by weight fr
4,4-diphenyl methanediisocyanate; and 6.4 mass% of 1,4-butanediol by means of a multi-screw extruder (matrix temperature: 260 ° C) for 20 min. This thermoplastic polyurethane resin was designated as TPU (B-3) (density: 1.16 g / cm ³ ; Drain A hardness: 75). The TPU (B-3) thus obtained was used as a pellet (B3a).
(Production Example 20: Pellet Example (B-1-1-3b)) [00325] With 100 parts by mass of TPU (B-3) obtained as described above, 0.27 parts by mass of magnesium stearate were mixed molten by means of a biaxial extruder to produce a pellet (B-1-3b). The magnesium ion content in the pellet (B-1-3b) was 110 ppm.
(Production Example 21: Pellet Example (B-1-4a)) [00326] A thermoplastic polyurethane resin (TPU) was produced by kneading by melting a mixture of: 80.6% by weight of polite
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125/158 tramethylene glycol with 2.0 groups of hydroxyls per molecule and an average number of 2,000 molecular weight; 17.0% by weight of
4,4-diphenyl methanediisocyanate; and 2.4 mass% of 1,4-butanediol by means of a multi-screw extruder (matrix temperature: 260 ° C) for 20 min. This thermoplastic polyurethane resin was designated as TPU (B-4) (density: 1.16 g / cm ³ ; hardness of Strut A: 65). The TPU (B-1-4) obtained in this way was used as a pellet (B-
1- 4a).
(Production Example 22: Pellet Production (B-2-1a)) [00327] In a 10 L canistered pressure autoclave equipped with an agitator, 5.3 kg of distilled water, 1.390 g of hexamethylenediamine solution ( 80% by mass), 1,030 g of isophthalic acid and 440 g of terephthalic acid, and the mixture was stirred until homogeneously dissolved by stirring, and 5.3 acetic acid was further added to it. After replacing the air in the autoclave with nitrogen, heating and stirring were started, and the water was distilled until the nylon salt concentration became 90% by mass while maintaining the internal pressure of 2.5 kg / cm G. Then , the heating was still continued in such a way that the internal pressure became 13 kg / cm G, and then the internal temperature was raised until reaching 250 ° C, while additionally distilling water. After that, the pressure gradually dropped, and finally the polymerization was carried out under a condition with a reduced pressure of 700 Torr for 1 hour. Then the pressure was raised to normal pressure. The product was removed from a nozzle at the bottom of the autoclave like a ribbon, followed by cutting. In this way, the resulting pellet was dried under reduced pressure to give 6I / 6T nylon. Polyamide was designated as PA (B-
2- 1). A proportion (isophthalic acid unit (I) / terephthalic acid unit (T)) of the number of isophthalic acid units in PA (B-21) was 70/30 (molar ratio). In addition, the relative viscosity was
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126/158
2.3, and the number of terminal carboxy groups was p / g. In this way resulting PA (B-2-1) (densitil.19 g / cm) was used as a pellet (B-2-1a).
(Production Example 23: Pellet Production (B-2-1a) [00328] With 100 parts by weight of PA (B-2-1 obtained as described above), 0.37 parts by weight of sodium stearate were mixed fused using a biaxial extruder to produce a pellet (B-2-1b). The sodium ion content in the pellet (B-2-1b) was 140 ppm. (Production Example 24: Pellet Production (B- 2-2a)) [00329] 1,088 g of ε-caprolactam, 363 g of ω laurylactam, and 36 g of distilled water were loaded into a 5 L high pressure autoclave equipped with a stirrer. After replacing the air in the autoclave with nitrogen, heating and stirring were started and the temperature was raised to 260 ° C. Polymerization was left with stirring, while regulating the pressure to 35 kg / cm G for 2 hours, after which the pressurized state was released for 2 hours until reach normal pressure, and finally the polymerization was carried out under a condition with a reduced pressure of 380 Torr po r 1 hour After the pressure was raised to normal pressure, the product was removed from the nozzle at the bottom of the autoclave like a tape, followed by cutting. In this way the resulting pellet was dried under reduced pressure to give a 6/12 nylon copolymer. The polyamide was designated as PA (B-2-2). The mass ratio (6 units / 12 units) from 6 units to 12 units in PA (B-2-2) was 75/25 (mass ratio). In addition, the relative viscosity was 2.3 and the amount of terminal carboxyl groups was 41 peq / g. The resulting PA (B-2-2) (densitil.10 g / cm) was used as a pellet (B-2-2a).
(Production Example 25: Pellet Production (B-2-2b) [00330] With 100 parts by weight of PA (B-2-2) obtained as described above, 0.27 parts by weight of magnesium stearate were mis
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127/158 castings using a biaxial extruder to produce a pellet (B-2-2b). The magnesium ion content in the pellet (B-2-2b) was 110 ppm by mass.
(Production Example 26: Pellet Production (B-2-3a)) [00331] In a high pressure autoclave equipped with a stirrer, an aqueous solution prepared by dissolving 60 parts by mass of ε-caprolactam, and 0.0063 was loaded part by mass of monohydrogen phosphite disodium pentahydrate in 2 parts by mass of desalinated water. After replacing the air in the autoclave with nitrogen, heating and stirring were started, and the temperature was raised to 280 ° C. Polymerization was carried out while regulating the pressure to 36 kg / cm G with stirring for 2 hours. After that, the pressurized state was released for 2 hours until it reached normal pressure, and finally the polymerization was carried out under a condition with a reduced pressure of 400 Torr for 1 hour. After the pressure was raised to normal pressure, the product was extracted from the nozzle at the bottom of the autoclave like a tape, followed by cutting. The resulting pellet was dried under reduced pressure to give a 6-polymer nylon. Polyamide (density 1.14 g / cm) was designated as PA (B-23). The relative viscosity of PA (B-2-3) was 3.8, and the sodium ion content was 1 ppm. PA (B-2-3). The pellet (B-2-3a) had a Vicat softening temperature of 190 ° C, and a melting point of 210 ° C.
(Production Example 27: Pellet Production (B-2-3b)) [00332] With 100 parts by weight of PA (B-2-3b) obtained as described above, 0.27 parts by weight of magnesium stearate were mixed melted using a biaxial extruder to produce a pellet (B-2-3b). The magnesium ion content in the pellet (B-2-3b) was 110 ppm by mass. In addition, the pellet softening point (B-2-3b) was 190 ° C, and the melting point was 210 ° C.
(Production Example 28: Pellet Production (B-2-4a))
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128/158 [00333] For a reaction flask featuring a stirrer equipped with a nitrogen feed port, in a distillation tube and a crucible to load a catalyst, 2,020 parts by mass of polyoxyethylene glycol having a molecular weight number were added average of 2,000, 860 parts by weight of polyoxytetramethylene glycol having an average molecular weight number of 1,800, 248 parts by weight of terephthalic acid, 1,300 by weight of ε-caprolactam and 8 parts by weight of pentaerythritiltetraquis [3- (3,5 -di-t-butyl-4-hydroxyphenyl) propionate] and the reaction was left under reduced pressure of 500 Torr at 250 ° C for 3 hours. Subsequently, the reduced pressure was gradually raised to distill unreacted ε-caprolactam, and thereafter a liquid prepared by dissolving 8 parts by mass of tetrabutoxy zirconium in 50 parts by weight of ε-caprolactam was added to the reaction vessel of a crucible of the catalyst under reduced pressure, then leaving the reaction at 260 ° C and 1 Torr for 2.5 hours. The product was removed from the spout at the bottom of the reaction flask as a strip, followed by cutting. In this way the resulting pellet was dried under reduced pressure to give a polyamide elastomer. Polyamide (density: 1.18 g / cm) was designated as PA (B-2-4a). The resulting PA (B-1-4) was used as a pellet (B-2-4a). The zirconium ion content in the pellet (B-2-4a) was 420 ppm.
(Production Example 29: Pellet Production (B-2-4b)) [00334] With 100 parts by weight of the PA (B-2-4) obtained as described above, 0.27 parts by weight of cobalt stearate were mixed melted by means of a biaxial extruder to produce a pellet (B-2-4b). The cobalt ion content in the pellet (B-2-4b) was 110 ppm. (Production Example 30: Pellet Production (B-3-1a)) [00335] Low density polyethylene with an MFR of 2.4 g / 10 min (190 ° C, under load of 2,160 g) and a density of 0.92
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129/158 g / cm in an amount of 100 parts by weight, 12 parts by weight of maleic anhydride, and 330 parts by weight of t-butylbenzene were mixed, and an atmosphere of nitrogen was provided, followed by dissolving the low density polyethylene at 160 ° C. Following dissolution, a mixture of 1.7 parts by weight of di-t-butylperoxide and 17 parts by weight of t-butylbenzene was added to this while stirring to allow the reaction for 2 hours. Then, the reaction liquid was removed, and stirred at room temperature to precipitate the resin as a powder. The powder thus obtained was washed with acetone, followed by vacuum drying to give an adhesive resin (B-33) which is a copolymer of ethylene vinyl acetate modified by maleic anhydride of white powder.
[00336] Subsequently, 100 parts by mass of the adhesive resin (B-3-3) resulting in this way, and 900 parts by mass of ethylene vinyl acetate copolymer which is the same as that used in the step mentioned above, were subjected to melting by mixing a biaxial segment type extruder to give a pellet (B-3-1a). (Production Example 31: Pellet Production (B-3-1b)) [00337] Regarding the 100 parts by mass of the pellet (B-3-1a) obtained as described above, 0.19 parts by weight of stearate of sodium were mixed melted using a biaxial extrusor to give a pellet (B-3-1b). The sodium ion content in the pellet (B-3-1b) was 140 ppm. (Production Example 32: Pellet Production (B-3-2a)) [00338] A copolymer of ethylene 1-butene having an MFR of 1.1 g / 10 min (190 ° C, under load of 2,160 g), a density of 0.92 g / cm, and a 1-butene content of 4 mol% in an amount of 100 parts by weight, 12 parts by weight of maleic anhydride, and 330 parts by weight of t-butylbenzene were mixed , and a nitrogen atmosphere was provided followed by dissolving the ethylene 1-butene copolymer at 160 ° C. Following dissolution, a mixture of 1.7
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130/158 parts by mass of di-t-butylperoxide and 17 parts by mass of tbutylbenzene was added to this while stirring to allow the reaction for 2 hours. Then, the reaction liquid was removed, and stirred at room temperature to precipitate the resin as a powder. In this way, the obtained powder was washed with acetone, followed by vacuum drying to give an adhesive resin (B-3-2) which is a copolymer of ethylene 1-butene modified by maleic anhydride of white powder.
[00339] Subsequently, 100 parts by mass of the adhesive resin (B-3-2) resulting in this way, and 900 parts by mass of the ethylene copolymer 1-butene, which is the same as that used in the step mentioned above, was subjected melt mixing in a biaxial segment type extruder to give a pellet (B-3-2a). (Production Example 33: Pellet Production (B-3-2b)) [00340] With respect to 100 parts by weight of the pellet (B-3-2a) obtained as described above, 0.28 parts by weight of stearate magnesium were mixed melted using a biaxial extruder to give a pellet (B-3-2b). The magnesium ion content in the pellet (B-3-2b) was 100 ppm.
(Production Example 34: Pellet Production (B-3-3a)) [00341] A copolymer of ethylene vinyl acetate featuring an MFR of 3.0 g / 10 min (190 ° C, under load of 2,160 g) , a density of 0.935 g / cm, and a vinyl acetate content of 15% by weight in an amount of 100 parts by weight, 12 parts by weight of maleic anhydride, and 330 parts by weight of t-butylbenzene were mixed, and a nitrogen atmosphere was provided, followed by the dissolution of the ethylene-vinyl acetate copolymer at 160 ° C. Following dissolution, a mixture of 1.7 parts by weight of di-t-butylperoxide and 17 parts by weight of t-butylbenzene was added to this while stirring to tolerate the reaction for 2 hours. Then, the reaction liquid was removed, and stirred at room temperature to precipitate the
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131/158 resin in powder form. The powder thus obtained was washed with acetone, followed by vacuum drying to give an adhesive resin (B-33) which is a copolymer of ethylene vinyl acetate modified by maleic anhydride of white powder.
[00342] Subsequently, 100 parts by mass thereby resulting in adhesive resin (B-3-3), and 900 parts by mass of ethylene vinyl acetate copolymer which is the same as used in the step mentioned above, were subjected the molten mixture in a biaxial segment type extruder to give a pellet (B-3-3a) (Production Example 35: Pellet Production (B-3-3b)) [00343] Regarding 100 parts by mass of pellet (B-3-3a) obtained as described above, 0.19 parts by weight of sodium stearate were mixed melted using a biaxial extruder to give a pellet (B-3-3b). The sodium ion content in the sample (B-3-3b) was 140 ppm. Example 1 [00344] The pellet (A-1) and the pellet (B-1-1a) were supplied to a coextruder in melted states at 210 ° C, with a 17-layer feed block like that of the multilayer structure was formed that included eight layers A and nine layers B alternately with the resin composition that constitutes each pellet, and coextruded to allow interflow, thus a laminated multilayer (inner coating) was produced. The thickness of the channel of each layer was varied in order to gradually increase in the feed block from the side of the front face towards the middle side, in this way the fusion of the pellet (A-1) and the pellet (B-1-1a) ) that flowed out were extruded in such a way that each layer of the extruded multilayer structure has a uniform thickness. In addition, a cut shape has been designed to give approximately the same thickness as layer A and layer B, which are adjacent to each other. The laminate consisting of 17 layers in total, DisPetition 870190056670, from 19/06/2019, p. 135/172
132/158 The obtained way was maintained to have a surface temperature of 25 ° C, and solidified by rapid cooling in a casting drum that was electrostatically applied. The molten film obtained by solidification through rapid refrigeration was subjected to compression by ligating on an exfoliated paper and then rolled up. It should be noted that the shape of the cane and the total amount of discharge were predetermined in such a way that the time period of about 4 min elapsed between the interflow of fusions from the pellet (A-1) and the pellet (B-11a) until solidification by rapid cooling on the casting drum.
[00345] As a result of observing a cross section of the molten film obtained as described above with DIGITAL MICROSCOPE VHX-900 (manufactured by KEYENCE CORPORATION), a multilayer structure showing an average thickness of each layer A and layer B being 1 pm, and an average thickness of the whole being 17 pm was revealed. It should be noted that each thickness was an average of measurements at nine randomly selected points.
Examples 2 to 60, and Comparative Examples 1 to 34 [00346] Multilayer structures according to Examples 2 to 60, and Comparative Examples 1 to 34 were produced in a similar manner to Example 1 except that the pellet type, state of lamination, temperature forming coextrusion, and the type and content of the metal salt as shown in Table 1 to Table 5 and Table 7 were employed.
[00347] In the Table, Table 2, Table (and Table 10, the melt viscosity represents a melt viscosity at 210 ° C, while in Table 4 and Table%, the melt viscosity represents a melt viscosity at 220 ° C. It should be noted that in Table 6, the melt viscosity at 210 ° C of each resin used in Examples 23
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133/158 to 38 and Comparative Examples 12 to 16 is shown together with. In addition, the melt viscosity shown in Table 3, Table 7, Table 8 and Table 11 shows a melt viscosity at a temperature being formed by the coextrusion of each Example and Comparative Example (that is, the temperature higher than the temperature of Vicat softening of the layer A resin composition by 30 ° C).
(Method for Evaluation of Multilayer Structure Characteristics) [00348] Each of the characteristics of multilayer structures obtained in Examples 1 to 60 and Comparative Examples 1 to 34 was evaluated according to the following method. The results of the evaluation of these characteristics are shown in Table 1 to Table 5 and Table 7 to Table 11 together with the proportion of components, physical properties, and the like in layer A and layer B.
(1) Melting viscosity of the resin composition constituting each layer [00349] The melting viscosity of the resin composition constituting layer A and the resin composition constituting layer B at predetermined temperatures was measured on a melted sample pellet using Capillographic (manufactured by Toyo Seiki Seisaku-sho, Ltd., model IC).
(2) Appearance of multilayer structure [00350] The presence / absence of correction of flow, risk, and fisheye of the multilayer structures obtained, were confirmed by visual inspection. The appearance of multilayer structures was determined according to the following criteria:
A: flow correction, streak and fisheye being almost absent;
B: flow correction, streak and fisheye being present, but a little;
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C: correction of flow, streak and fisheye being markedly present; and
D: flow correction and streak are notable, with a large number of fish eyes present.
(3) Multilayer Structure Oxygen Transmission Rate [00351] Moisture conditioning the obtained multilayer structure was carried out at 20 ° C and 65% RH for 5 days, and two sample pieces of the conditioned multilayer structure were structures provided to measure the oxygen transmission rate using MOCON, model OX-TRAN2 / 20 manufactured by Modern Controls, Inc., under a condition involving 20 ° C and 65% RH according to a JIS K7126 method (isopathic method), and the mean was determined (unit: mL · 20 pm / m ² · day · atm).
(4) Oxygen transmission rate after flexing the multilayer structure [00352] In a manner similar to that described above, the oxygen transmission rate of the multilayer structure was determined according to ASTM-F392-74 after repeated flexing 500 times using Gelbo-Flex Experimenter manufactured by Rigaku Kogyo Co., Ltd.
(5) Flex resistance of multilayer structure [00353] According to ASTM-F392-74, the flexion was repeated using Gelbo-Flex experimenter manufactured by Rigaku Kogyo Co., Ltd., and the number of times the flexion repeated up to a hole through (microporosity) was first observed.
(6) Layer Strength Between Layers Between Layer A and Layer B in the multilayer structure [00354] The adhesive interlayer strength between layer A and layer B of the multilayer structure was determined as follows.
Moisture conditioning of the multilayer structure obtained was repeated 870190056670, dated 06/19/2019, p. 138/172
135/158 in an atmosphere involving 23 ° C and 50% RH for 7 days, followed by cutting to give a section of strips having a width of 15 mm as a measurement sample. In this measurement sample, the peeling force of the T- matrix was measured in an atmosphere involving 23 ° C and 50% RH, using an AGS-H autograph model manufactured by Shimadzu Corporation in a tension range of 250 mm / min . The value thus obtained (unit: g / 15 mm) was determined as the interlayer adhesive strength between layer A and layer B.
(7) Stretching of multilayer structure [00355] The multilayer structure in this way obtained was mounted on a pantograph type biaxial stretching apparatus manufactured by Toyo Seiki Seisaku-sho, Ltd., and the simultaneous stretching was carried out at 100 ° C with a proportion traction 4 x 4 times. The appearance of the elongated film was assessed according to the following evaluation criteria.
A: lack of uniformity and thickness of the locally irregular wall not being found;
B: slight lack of uniformity or thickness of the locally irregular wall being found, but being practically problematic;
C: certain sizes of unevenness or locally irregular wall thickness being found; and
D: development or disruption of the multilayer structure being encountered.
(8) Multilayer structure thermoformability [00356] The multilayer structure obtained in this way was subjected to thermoforming using a thermoforming machine (a deep vacuum pressure tracing the molding of the machine model FX-0431-3 manufactured by Asano Laboratories Co. Ltd .,) in a
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136/158 round cup shape (matrix shape: top: 75 mm; bottom: 60 mm; depth: 30 mm; and stroke ratio S = 0.4) at a film temperature of 120 ° C with compressed air (atmospheric pressure: 5 kgf / cm ² ) to give a thermoformed bottle. The training conditions employed in this process were as follows.
Heater temperature: 400 ° C;
buffer: 45φ x 65 mm; buffer temperature: 100 ° C; and matrix temperature: 70 ° C.
[00357] The appearance of the thermoformed flask obtained as described above was evaluated according to the following evaluation criteria.
A: Lack of uniformity, cracking, and locally irregular wall thickness not being found;
B: slight lack of uniformity, cracking or thickness of the locally irregular wall being found, but not practically problematic;
C: certain size of lack of uniformity, cracking or thickness of the locally irregular wall being found; and
D: development of rupture of the thermoformed bottle being found, leading to the occurrence of deformation.
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unity Ex. Co-p.1 Ξχ. Cozr.p.2 Zx. Con.p.3 Ex. Compo.4 Ex. Comp.5 il fl dTheANDfl U • d jJ> -iziANDfl M0 □ J fl d α S α U A wood resin A - EVüEI lA.-ll · Pellet type of bucket A - TO 1 TO 1 A-B A-9 A-1D Content of ethylene units í in “o_ 32, E 32, E 32, E 32, E 32, 5 Degree of saponification í in “o_ 99, E 99, E 99 „E 99, E 99.5 Phosphate compound content PP · 4E 45 43 9D 45 Azetate content PP 1ED 15D ! D 13,500 150 Boron compound content PP 260 260 260 250 E.QDD Fusion viscosity | q;>) Pi - s 3.1D0 3. GONE 3.BDD 970 49.5DD Melting viscosity (l ^ y.) Pi - s 5DD 5DD 590 9D 1.2DD fl / 21 l ^ glD {τι., / η.,) - -a, ss6 -0, 694 -0, 404 -0.516 -0, ãDB KFR ^119Π:, 2160 g) q / 10 -in 1, D 1, B 1.6 6, E: D, 05 Mun.ero of limitations of can. A - 1 2 B .g 9 Average layer A thickness JJT. 5 5 1 1 1 Zetal species - Mi Kx - fl fa Equivalent content of metal element | Motorcycle B PP 140 140 - 23.DOO 140 0 jJ11 CJJ IDα • d αE α U Falling resin. - TPU JE-1-1) Pellet type of hunting B - E-l-la E-l-la E-l-la E-l-la E-l-la Melting viscosity | q _ls ) And the 1,430 1,400 1.4DD 1.40D 1.40D Fusion viscosity And the 230 230 23D 230 230 fl / 2l · LoglD ^ _2H / q _LS ) - -O, 392 -0.592 -0.392 -O ,, 392 -0.392 Rolling mill of can.ida B - 2 5 9 9 9 Average layer E thickness JJT. 4, E 5 1 1 1 Zretal species - - - - - - Equivalent content of methyl element | Auction 2 | · PP - - - - -8 fl • d • d> -ifl + J £ Total structure thickness in multiple layers JJT. 17 19 17 17 17- a, 46 0.46 0.39 2.56 D, 19 equivalent content of methyl element | Moti 3 [ PP 66 74 D 10,600 66 •1- í- «□ iparenzia - AND B THE D D Oxygen transmission sandpaper Lot 4! · 1, 2 1 a, 9 110 170 Oxygen transfer taxi after flexion jMoto 42 0 200 21D E6ü 630 Flexion kesistenzia teir.po 300 400 45D 250 200 Adhesive layer strength between layer A and cimadi £ g / 15 mm 760 790 190 2 60 400 Elasticity - D Ç B D D Thermoformability - D Ç B D D
Kotas 1 and 2: The equivalent complexion of ir.ital element ^rr zz> zr.o referred to herein means the proportion of mass of e_ezentz 'by rritil incluidr · nr · sil de mstal zzmtídz · in the resin composition of each can .id i or can.ida E- with respect to the mass of the composition of the acidic resin canid.
Kota 3: 0 * equivalent content of mstil 'ζζστ.ζ · here reference.z.dz · meaning the proportion · of mass of element of inluded material nz> silal of netal contained the totality of the multi-dimensional structure ~ relation to the total mass structure and multilayer.
t-Tota 4: ir.L 2D pz / m ^S di.a atn.
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Table 5
unity Ex. Corp.12 Ex. Corp.L3 Ex. Cor.p.13 Zx. Cor.p. L5 Zx. Cor.p.16 41laughsU xl a laughkl• 1 x ·•1kl xlΙΛ M * laughsYOUlaughs1u Layer A kesina - EVDR | A-1) Pellet type of face A - TO 1 TO 1 A-B A-9 A-LD Content of ethylene units % err. r.ol 32, E 32, E 32, E 32, Ξ 32, 5 Saponi degree Hey zaçào % e- r.ol 99, E 99.5 99.5 99.5 99.5 Color content. Phosphate compound ppm 45 45 35 90 35 Acetate content ppm 150 150 ID 15,500 L5D Boron zomposite content ppm 26D 240 26D 2 5D 5.DDD Fuslo viscosity ΙηίΑ, Τ Pa - s 2,790 2.7 90 O. 42D B D 34,553 Melting viscosity | q _2A 'l · Pa s 350 350 530 30 l.DED 1l / 2 | i logLD <γ _λ ^ιγ / ι | ι * ^{, τ} » - -D, Ϊ96 -0, 396 -0, 405 -0.519 -0.903 MFT. (19DC, 2L60 g) g / 10 r.in 1, B 1, B 1, 6 6, E 0.05 lamination tamer of zamada A - L 2 9 3 3 Average thickness of layer A9 5 1 1 1 Species of r.etal - L ”1 Ka - aunt Bad Equivalent element content of r.etal ItTota 1) ppm 140 140 - 25,000 130 laughs IT a d E-layer resin - PA | B-2-lh Pellet type of face E - Ε-2-la Ε-2-la Ε-2-la Ε-2-la Ε-2-la Fuslo viscosity Ιη ^ Τ Pa - s 1.5E0 L.5E0 1.5ED L. E5D 1.E50 Fuslo viscosity Pa - s 350 350 350 3 50 450 | 1/2 | <logLD (Γυ ’/ ηυΊ - -D, 2E9 -0.249 -D, 2 69 -D, 269 -D, 269 Number of limitations of zamada E - 2 3 9 9 9 Average thickness of layer E3, 5 3 1 1 1 Species of r.etal - - - - - - equivalent e-content content ofr.etal | Kota 2) ppm - - - - - 41laughs ITlaugh xl□ Total structure thickness in rrxilt i loaded F * 17 L9 17 17 17 Πχ » ^ΙΓ / ⁼ Ι aa. ' - L 1 0, E5 5.65 0.42 equivalent r.etal element content | Kota 3) ppm 66 74 0 10,900 66 Temperitura de Eorzraçlo by coextruslo *Ç 250 •Sü ΐ fl • d> -lfl £appearance - AND 0 THE D D ΙΊ Oxygen transmission Tii jMota Jl · 1.2 1 D, 9 110 L7D U • d · * Oxygen trinsmisslo rate ip6s flexlo jMota Jl · 32 0 290 210 560 630 • d,1 Resistance to Elexlz · term 240 320 j6d 2 30 L40 I read Μ Adhesive force Interzamated between layer A and zazrada E g / 15 -J, 300 330 200 2 D 42 0 u Elasticity - D Ç AND D DTerr.oEorr.abilidade - D Ç AND D D
Mz «tas 1 and 2: ü * equivalent content of metal element 'zz« mz · referenced here · means the mass representation of elementz · zretal included · in the metal salt contained in the resin body of each cart to or from zarada And color. ratio of the composition of zada zamada resin.
Moti 3: ü * equivalent metal content 'zz> mo a> referred to above means the proportion of the rectal element mass included in the zretal salt contained in the whole multilayer structure with respect to the total mass of the ezr structure. r.ulticaradas.
Mota 4: mL 20 pm / rr. ² day atm
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Table 13
unity Zx. Conp.23 Zx. Conp.24 Zx. Corrp.23 ZX. LZCTp. 2b Zx. LZCTp.2i Zx. Cexp.2B II n §u□ANDd□ youH ti ld 411su Fe caxada A - EVOH (A-l | ZVffl (A-141 Pellet tip of cart A - A-l A-l A-B A-9 A-10 A-14 Too: from ethylene units 1 The nol 32, E 32, E 32.5 32.5 32.5 32.5 l, zjj de sanoni ricaçao 1 en nol 59, E 39, E 39, 5 35.5 35.5 35.5 Teo: de Fz P ;s 43 43 s: 43 43 Too: da azotato 7F ' 153 153 9: 13.3: 3 153 1C5 Too: from boron cztrpoito 7F ' 263 263 26-3 233 5.:3: 230 Iusium viscosity (huJ at 3.13: 3.13: 3.13: 913 43.5: 3 2,300 Iusium n id viscosity Jai 333 333 333 s: 1.23: 413 [1/2) loglO (Vii *) - -3.356 - :, 356 - :, 4: 4 - :, 316 -: _γ β: β - :, 335 MFR (19: * C, 216: q | g / lfl nin :.B :.B 1, Í> M 0.05 4. And Lanina number; carriage A - 2 3 3 3 3 2 Round thickness of whitewash A | .IT. 4 3 1 1 1 5, 1 Total thickness of whitewash A | .IT. 5 3 3 3 13.2 Christmas Eapacies - Shah Shah - Ka Ka I do Content here applies to the ne tal's errant (Note 1) 7F ' 143 143 - 23.c: o 143 125/43: u11 s u E- whitewash resin - adhesive ream (3-3-1) Προ of the pallet of the cart 3 - 3-3 it 3-3 it 3- 3 it 3-3 it 3-3 it 3-3 it Viscosity of Jjslo (iii.il Jai 1.B3: 1.B3: 1.13: 1.13: 1.13: 1,133 Iaslo viscosity (ijJ Jai 273 273 2Ί 3 213 213 213 [1/2) loglO [Vm) - -3,412 - · :, 412 412 - · :, 412 412 - :, 412 Nüiaro da lanina; tas da cartada 3 - 1 2 1 1 1 1 Thickness of whitewash E I.IT. 5 4 1 1 1 16 Total thickness of the whitewash E Ι.ΙΓ. 5 B 1 1 1 16 Christmas species - - - - - - - Too: equivalent of Neta's e.eionto. i, motorcycle3)- - - - - - 3 sec4 il xj í Total amount of the rrultizanadas estzjtjra I.IT. 17 17 17 li li 26.2 W 1 - 3.34 3.34 ¢, 46- 3 C, 23 C, 51 Too: equivalent of the election of Metal (Note3)6b 7412.2: 0 74 23 M íü ΙΊ ti rtJl ¹¹ h J ü «II u Aparénzzj - and AND THE D D THE Oxygen transfer rate (Xota 4 | 1.2 1 C, 9 113 113 0 Rate of oxygen transfer jpos FLiXÍO (Xota 4 | 443 313 26-3 333 633 1CE Flexion resistance te προ 333 433 4: 3 2: 3 2: 3 4: 3 “Zntercanada adhesive area between zanada A and cart 3 g / 15 γτπ 713 743 113 26-3 313 633 Elasticity - D Ç AND- D D Z · Te no Fornaii da da - D Ç AND· D D Z · Xotas 14 2: The equivalent content of the το errant included in the natal salt included in the tal ': orro resin of here roiori ·: every cure sigmiica to or canada proposed: color B. relap of potassium and The potassium of element ofrornõsLçSõ - resin metal
da: ada zarrada.
Xota 3: c · ⁿ taor eqjiv alonanto da netal 'zocto aq-Jl reiaride sigriiFz-za the proportion of the lassa of the oletiento da iretal included the total rectal salt contained in the totality of the rTultizanado ζζσ. the total amount of oxytricized x rolled.
Xota 4: il · 23 μΐ .- 'ζ · Dza atn
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148/158 [00358] From the results shown in Table 1 to Table 5 and Table 7 to Table 11, it is concluded that the adhesion of the upper interlayer can be achieved in a multilayer structure presenting layer A constituted with a composition of resin containing a gas barrier resin, and layer B consisting of a resin composition containing a thermoplastic resin, and including at least 8 laminated layers, when not less than 1 ppm and not more than 10,000 ppm of a metal salt is contained in at least one of the resin compositions, included in layer A to layer B which are adjacent to each other. In addition, it is also concluded that high flexural strength is achieved in this way, and furthermore, a low rate of oxygen transmission can be maintained even after flexing. In addition, superior elongation capacity and thermal formability will also be suggested.
[00359] On the other hand, according to Comparative Examples 1, 2, 6 to 8, 12, 13, 17 to19, 23, 24, 3 28 to 31 in which the multilayer structure including less than eight laminated layers exhibited rate significantly increased oxygen transmission after flexion, indicating less resistance to flexion. In addition, stretching and thermoformability were also lower. According to Comparative Examples 3, 9, 14, 20, 25, 32 and the like, in which both layer A and layer B contain no less than 1 ppm of a metal salt in the resin composition, the realization sufficient adhesive strength failed, and delamination between layers was developed in the flexural strength test, and the increase in the oxygen transmission rate after flexion was remarkable, also indicating less resistance to flexion. According to Comparative Examples 4, 15 and 26 where the layer A resin composition contained a metal salt in an amount in excess of 10,000 ppm, EVOH significantly decomposed, thereby leading to a lack of
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149/158 stable melting viscosity in the formation, and thus it was difficult to obtain a film showing a multilayer structure in a favorable state. In this way, the oxygen transmission rate of those exhibited, oxygen transmission rate after flexion and flexion resistance are all lower, and the adhesion was also lower in strength due to the breaking of the EVOH layer material. Furthermore, as these films having a multilayer structure had lower elongation quality before stretching, elongation and thermoformability were also inferior. According to Comparative Examples 5, 16 and 27 where the melt viscosity Q1a was more than 1 x 10 ⁴ Pa ^ s; (1/2) logw (Π2α / γ | 1α) was less than -0.8; er | 2B / r | 2A was less than 0.3, EVOH compatibility and the thermoplastic resin, in terms of viscosity, was wrong, so it was difficult to obtain a film presenting a multilayer structure in a favorable state. In addition, for the same reasons, they exhibited low adhesion between layers, and all lower oxygen transmission rates, oxygen transmission rate after flexion, and flexural strength. In addition, as the quality of these films presenting a multilayer structure before stretching was inferior, they were also inferior in stretching and thermoformability.
Example 61 [00360] A laminate (polypropylene / adhesive resin / (multilayer structure consisting of 33 alternating layers of TPU (B-1-1b) and EVOH (A-1)) / adhesive resin / polypropylene) in which a multilayer structure and a layer of thermo plastic resin was laminated was produced using the following four types of 378-layer coextrusion apparatus, under the conditions described below. The construction of the plate included 100 pm of a multilayer structure presenting 33 layers with an alternating constitution of TPU (B-1-1b) and EVOH
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150/158 (A-1), 50 pm of an adhesive resin layer, and 800 pm of a polypropylene layer. It should be noted that the layer (TPU / EVOH presenting 33 layers with an alternating constitution, the pellet (B-1-1b) and the pellet (A-1) were supplied to a coextruder in melted states at 220 ° C with a block fed by 33 layers in such a way that the multilayer structure is formed that includes 17 layers B and 16 layers A alternately with the resin composition that constitutes each pellet, and coextruded to allow interflow, in this way a multilayer laminate was produced. of each layer was varied in order to gradually increase in the feed block from the side of the front face towards the middle side, in this way the pellet (B-1-1b) and the pellet (A-1) merged were merged. extruded in such a way that each layer of the extruded multilayer structure has a uniform thickness, in addition, a slit shape has been designed to give approximately the same thickness as layer A and layer B which are adjacent to each other. outermost layer of the TPU / EVOH layer which includes 33 layers with an alternating constitution was produced to give a lamina showing a TPU (B-1-1b) consisting of the pellet (B-1-1b).
[00361] Conditions for forming coextrusion were as follows:
Layer structure: polypropylene / adhesive resin / (the multilayer structure featuring 33 layers with an alternating constitution of TPU (B-1-1b) and EVOH (A-1) / adhesive resin / polypropylene
Extrusion temperature of TPU pellet (B-1-1b) and EVOH pellet (A-1): cylinder resin feed portion / cylinder upstream portion / cylinder middle portion / cylinder downstream portion = 175/210/210/210 ° C
Extrusion temperature of the adhesive resin: Ali port Petition 870190056670, of 06/19/2019, p. 154/172
151/158 resin filling of part of the cylinder / portion upstream of the cylinder / portion of the middle of the cylinder / portion downstream of the cylinder = 170/170/210/210 ° C
Polypropylene extrusion temperature: resin feed port of part of the cylinder / portion upstream of the cylinder / portion of the middle of the cylinder / portion downstream of the cylinder = 170/170/220/220 ° C
Adapter temperature: 220 ° C
Supply block temperature: 220 ° C
Matrix temperature: 220 ° C
Matrix extruder specifications for each TPU and EVOH resin (two):
Extruder 40 model VSVE-40-24 (manufactured by Osaka Seiki Kosaku K.K.)
Adhesive resin:
Extruder 40 model 10VSE-40-22 (manufactured by Osaka Seiki Kosaku K.K.)
Polypropylene:
Extruder 65 model 20VS-65-22 (manufactured by Osaka Seiki Kosaku K.K.)
Matrix T:
650 mm wide (manufactured by Research Laboratory of Plastic Technology co., Ltd.)
Cooling roller temperature: 30 ° C
Extract temperature: 2 m / min [00362] Like the propylene resin, a mixture of Novatec PP EA7A and Novatec PP EG-7FT (prepared by Jpan Polyprolynene Corp.) in a mass ratio of 85: 15 was used, and as the adhesive resin, ADMER QF551, prepared by Mitsui Chemicals, Inc. was used.
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152/158 [00363] Moisture conditioning of the laminate, produced as described above, was carried out in an atmosphere involving 23 ° C and 50% RH for 30 days, followed by cutting to give a strip section having a width of 15 mm. The measurement of adhesive strength between layers [00364] Between the adhesive resin layer and layer A was 1.80 b / 15 mm, indicating favorable adhesion. In the strip section as a measurement sample, the resistance to peeling the T- matrix was measured in an atmosphere involving 23 ° C and 50% RH, using an AGS-H autograph model manufactured by Shimadzu Corporation at a tension rate of 250 mm min. The value thus obtained (unit: g / 15 mm) was determined as the adhesive strength between layers between the adhesive resin layer and layer A.
[00365] The laminate produced as described above was mounted on a pantographic biaxial stretching machine by TOYO SEIKI Co., Ltd., and simultaneously the biaxial stretching was carried out at 140 ° C with an extraction rate of 3 x 3 times for obtain a multilayer stretching film. The multilayer elongation plate exhibited favorable elongation, and after elongation, the favorable elongation film had no crack, lack of uniformity and non-uniform wall thickness, accompanied by the favorable appearance (in terms of transparency, gel or seed).
[00366] Moisture conditioning of the multilayer stretching film produced as described above was carried out at 20 ° C and 30% RH for one face, and at 95% RH with higher humidity for another face for 5 days. Two pieces of a conditioned multi-layer structure sample were provided to measure the oxygen transmission rate using MOCON, model OX-TRAN10 / 50 ³ manufactured by Modern Controls, Inc., under a condition involving 2 ° C and 30%
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RH and 100% RH respectively, according to a method of JISK7126 (isopietic method), and the mean was determined. The amount of oxygen permeabilization of the multilayer elongation film of the present Example was 1.21 cc / m day atm, indicating a favorable gas barrier property.
[00367] In addition, the laminate obtained as described above was subjected to thermoforming with a thermoforming machine (a molding machine for deep pressure vacuum filling capacity model FX-0431-3 manufactured by Asano Laboratories Co., Ltd .) in a cup shape (mold shape: top: 75 mm; bottom: 60 mm; depth: 75 mm; and extraction rate S = 1.0) at a plate temperature of 140 ° C with compressed air (atmospheric pressure: 5 kgf / cm) to give a transformed bottle. The training conditions employed were as follows: heater temperature: 400 ° C buffer: 45 x 65 mm;
buffer temperature: 120 ° C; and mold temperature: 70 ° C [00368] When the appearance of the transformed and thus obtained flask was visually observed, cracking, lack of uniformity and locally uneven wall thickness were not found, the elongation was perfectly level. In addition, superior transparency and favorable appearance were agreed.
Reference Example 1 [00369] A laminate was obtained in a manner similar to Example 61 except that the pellet (A-8) was used in place of the pellet (A-1), and the pellet (B-1-1a) was used in place of the pellet (B-1-1b). Using the resulting laminate, the adhesive strength between layers between the adhesive resin layer and layer A was determined in a similar manner to Example 61, and revealed a value of 220 g / 15 mm.
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Example 62 [00370] A laminate (PA (B-2-3a) / (multilayer structure having 33 layers with an alternating constitution of PA (B-2-2b) and EVOH (A-1)) / adhesive resin / polyethylene of low density polymerized at low pressure) in which a multilayer structure and a layer of thermoplastic resin were laminated, was produced using the following five types of 36-layer coextrusion apparatus, under the conditions described below. The construction of the plate included 60 pm of PA layer (B-2-3a), 40 pm of a multilayer structure showing 33 layers with an alternating constitution of PA (B2-2b) and EVOH (A-1), 20 pm of a layer of adhesive resin and 80 pm of a layer of low density polyethylene polymerized at low pressure. It should be noted that, as the PA / EVOH layer having 33 layers with an alternating constitution, the pellet (B-2-2b) and the pellet (A-1) were supplied to a coextruder in melted states at 210 ° C with a 33-layer feed block in such a way that a multilayer structure is formed that includes 17 layers B 3 16 layers A alternately with the resin composition that constitutes each pellet, and coextruded to allow interflow, thus a multilayer laminate was produced. The thickness of each layer was varied in order to gradually increase in the feed block on the side of the front face towards the middle side, thus merging the pellet (B-2-2b) and the pellet (A-1) which interflow have been extruded in such a way that each layer of the extruded multilayer structure has a uniform thickness. In addition, a strip-shaped shape was designed to give approximately the same thickness as layer A and layer B that are adjacent to each other. The outermost layer of the PA / EVOH layer, which includes 33 layers with an alternating constitution, was produced to give a laminate presenting a constitution with
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PA (B-2-2b) consisting of the pellet (B-2-2b).
[00371] Conditions for forming extrusion were as follows. [00372] Layer structure: PA (B-2-3a) (multilayer structure with 33 layers with an alternating constitution of P (B-22B) and EVOH (A-1) / adhesive resin / low density polyethylene polymerized by pressure low
PA extrusion temperature (B-2-3a): resin feed port of part of the cylinder / portion upstream of the cylinder / portion of the middle of the cylinder / portion downstream of the cylinder = 195/230/240/240 ° C
Extrusion temperature of PA (B-2-2b) and EVOH (A-1): resin feed port of cylinder part / portion upstream of the cylinder / portion of the middle of the cylinder / portion downstream of the cylinder = 175 / 220/230/230 ° C
Adhesive resin extrusion temperature: resin feed port of part of the cylinder / portion upstream of the cylinder / portion of the middle of the cylinder / portion downstream of the cylinder = 170/200/220/230 ° C
Extrusion temperature of low density polyethylene polymerized by low pressure: resin feed port of part of the cylinder / portion upstream of the cylinder / portion of the middle of the cylinder / portion downstream of the cylinder = 170/200/220/230 ° C
Adapter temperature: 240 ° C
Supply block temperature: 240 ° C
Matrix temperature: 240 ° C
Extruder and T die specifications for each PA (B-2-3a), PA (B-2-2b) and EVOH (A-1) resin (three):
Extruder 40 model VSVE-40-24 (manufactured by Osaka Seiki
Kosaku K.K.)
Adhesive resin:
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Extruder 40 model 10VSE-40-22 (manufactured by Osaka Seiki Kosaku K.K.)
Low density polyethylene polymerized at low pressure:
Extruder 65 model 20vs-65-22 (manufactured by Osaka Seiki Kosaku K.K.)
Matrix T:
650 mm width (manufactured by Reseach Laboratory of
Plastics Technology Co., Ltd.)
Cooling roller temperature: 30 ° C
Extraction speed: 10 m / min [00373] As the low pressure polymerized low density polyethylene resin, EVOLUE SP2520 manufactured by Prime Polymer Co., Ltd. It was used, and as the adhesive resin, ADMER NF558, manufactured by Mitsui Chemicals, Inc. was used.
[00374] Conditioning the moisture of the laminate produced as described above was carried out in an atmosphere involving 23 ° C and 50% RH for 30 days, followed by cutting to give a section in strips having a width of 15 mm. The measurement of the adhesive strength between layers between the adhesive resin and layer A was 1.670 g / 15 mm, indicating favorable adhesion. In the strip section as a measurement sample, T- matrix peel resistance was measured in an atmosphere involving 23 ° C and 50% RH, using an AGS-H autograph model manufactured by Poe Shimadzu Corporation at a tension rate of 250 mm / min . The value thus obtained (unit: g / 15 mm) was determined as an adhesive force between layers between the adhesive resin layer and layer A.
[00375] The laminate produced as described above was assembled in a pantographic stretching machine manufactured by TOYO SEIKI Co., Ltd., and simultaneous biaxial stretching was performed at
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140 ° C with an extraction ratio of 3 x 3 times to obtain a multilayer stretching film. The multilayer plate exhibited favorable elongation, and after elongation, the resulting multilayer elongation film had no groove, lack of uniformity and uneven wall thickness, accompanied by a favorable appearance (in terms of transparency, gel or seed).
[00376] Moisture conditioning of the multilayer stretching film produced as described above was carried out at 20 ° C and at 30% RH for one face. And at 95% RH with higher humidity for another face for 5 days. Two pieces from a sample of the conditioned multilayer structure were provided to measure the oxygen transmission rate using MOCON, model OX-TRAN10 / 50A manufactured by Modern Controls, Inc., under a condition involving 20 ° C, and 30% RH and 100 ° RH respectively, according to a JIS method K7126 (isopisthetic method), and the mean was determined. The amount of oxygen permeabilization of the multilayer elongation film of the present Example was 2.93 cc / m day atm, indicating a favorable gas barrier property.
[00377] Furthermore, the laminate obtained as described above was subjected to a thermoforming machine (a molding machine for deep pressure vacuum design model FX-0431-3 manufactured by Asano Laboratories Co. Ltd.,) in a cup shape (matrix shape: top: 75 mmp; bottom: 60 mmp; depth: 75 mmp; and extraction rate S = 1.0) at a plate temperature of 105 ° C with compressed air (atmospheric pressure : 5 kgf / cm) to give a thermoformed bottle. The training conditions employed were as follows:
heater temperature: 350 ° C buffer: 45 x 65 mm;
buffer temperature: 90 ° C; and
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158/158 matrix temperature: 50 ° C.
[00378] When the appearance of the thermoformed flask obtained in this way was visually observed, cracking, lack of uniformity and locally uneven wall thickness not found, and equally perfect elongation. In addition, superior transparency and favorable appearance were verified.
INDUSTRIAL APPLICABILITY [00379] As in the previous, the multilayer structure of the present invention is appropriately used for food packaging materials, various types of vials and the like, since superior characteristics such as gas barrier properties are maintained even against deformation such as stretching or bending.

权利要求:
Claims (19)
[1]
1. Multilayer structure, characterized by the fact that it comprises at least 8 layers of resin, with at least 8 layers of resin comprising:
(i) a plurality of layers A, each layer A comprising a resin composition comprising a gas barrier resin, and (ii) a plurality of layers B, each layer B constituted with a resin composition containing a thermoplastic resin, being whereas each of layers A and each of layers B is alternatively laminated in sequence;
the average thickness of a single layer of layers A, layers B or both layers A and B being not less than 0.01 pm and not more than 7 pm; and, in adjacent layers of layer A and layer B:
at least one of the resin composition in layer A and the resin composition in layer B comprises a metal salt, the metal salt content being not less than 1 ppm and not more than 10,000 ppm in terms of equivalent metal element, and an adhesive interlayer force between layer A and layer B being not less than 450 g / 15 mm.
[2]
2. Multilayer structure, according to claim 1, characterized by the fact that it has a thickness of not less than 0.1 pm and not more than 1,000 pm.
[3]
3. Multilayer structure, according to the claim
1, characterized by the fact that the metal salt is at least one selected from the group consisting of an alkali metal salt, a salt of
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2/6 alkaline earth metal, and a block d metal salt in group 4 of the periodic table.
[4]
4. Multilayer structure according to claim 1, characterized by the fact that the gas barrier resin is an ethylene-vinyl alcohol copolymer.
[5]
5. Multilayer structure, according to the claim
4, characterized by the fact that the content of ethylene units of the ethylene-vinyl alcohol copolymer is not less than 3 mol% and not more than 70 mol%.
[6]
6. Multilayer structure according to claim 4, characterized by the fact that the ethylene-vinyl alcohol copolymer has a degree of saponification of not less than 80 mol%.
[7]
7. Multilayer structure, according to the claim
4, characterized by the fact that:
the ethylene-vinyl alcohol copolymer comprises at least one selected from the group consisting of a structural unit (I) and a structural unit (II), and a content of the structural units (I) and (II), with respect to the entire structural units , is not less than 0.5 mol% and not more than 30 mol% - ch ₂ ch -, ¹ 3
R ¹ —C —R ³ (I)
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3/6 - CHaCH -
I ο
R ⁴ - C— R ⁶ (n)
IR ^s - C - R ⁷ I
OH being that in Formula (I) above,
R ¹ , R ² and R ³ are each independently a hydrogen atom, an aliphatic hydrocarbon group comprising 1 to 10 carbon atoms, an alicyclic hydrocarbon group comprising 3 to 10 carbon atoms, an aromatic hydrocarbon group comprising 6 to 10 atoms of carbons or a hydroxyl group;
two out of R ¹ , R ² and R ³ can bond with each other, unless two out of R ¹ , R ² and R ³ are both a hydrogen atom; and the aliphatic hydrocarbon group comprising 1 to 10 carbon atoms, the alicyclic hydrocarbon group comprising 3 to 10 carbon atoms and the aromatic hydrocarbon group comprising 6 to 10 carbon atoms optionally comprising a hydroxyl group, a carboxyl group or a halogen atom ; and, in Formula (II) above,
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, an aliphatic hydrocarbon group comprising 1 to 10 carbon atoms, an alicyclic hydrocarbon group comprising 3 to 10 carbon atoms, an aromatic hydrocarbon group comprising 6 at 10 carbon atom or a hydroxyl group;
R ⁴ and R ⁵ or R ⁶ and R ⁷ can bond with each other, unless both R ⁴ and R ⁵ or both R ⁶ and R ⁷ are a hydrogen atom;
the aliphatic hydrocarbon group comprising 1 to 10
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4/6 carbon atoms, the alicyclic hydrocarbon group comprising
3 to 10 carbon atoms and the aromatic hydrocarbon group comprising 6 to 10 carbon atoms optionally comprise a hydroxyl group, a group, a carboxyl group or a halogen atom.
[8]
8. Multilayer structure according to claim 1, characterized in that the layer A resin composition comprises a phosphate compound in an amount of not less than 1 ppm and not more than 10,000 ppm in terms of phosphoric acid group equivalent.
[9]
9. Multilayer structure according to claim 1, characterized by the fact that the layer A resin composition comprises a carboxylic acid in an amount of not less than 1 ppm and not more than 10,000 ppm.
[10]
10. Multilayer structure according to claim 1, characterized in that the layer A resin composition comprises a boron compound in an amount of not less than 1 ppm and not more than 2,000 ppm in terms of boron equivalent.
[11]
11. Multilayer structure, according to claim
I, characterized by the fact that the thermoplastic resin is at least one resin selected from the group consisting of thermoplastic polyurethane, polyamine, and an adhesive resin presenting a functional group capable of reacting with a group included in the gas barrier resin in the molecule.
[12]
12. Multilayer structure, according to claim
II, characterized by the fact that the thermoplastic resin comprises the adhesive resin, which is at least one resin selected from the group consisting of (i) a carboxylic acid modified polyolefin and a metal salt of a carboxylic acid modified polyolefin, (ii ) a thermoplastic resin comprising a group of borô acid Petition 870190056670, of 19/06/2019, p. 166/172
5/6 nico in the presence of a boronic acid or water, and (iii) a vinyl ester based copolymer.
[13]
13. Multilayer structure according to claim 1, characterized in that the resin composition of at least one selected from the group consisting of layer A and layer B has a melting viscosity (ιγ), as determined at a temperature 210 ° C and a shear rate of 10 / sec, not less than 1 x 10 ² Pa ^ s and not more than 1 x 10 ⁴ Pa ^ s, and a melting viscosity (ι 2), as determined at a 210 ° C and a shear rate of 1,000 / sec, not less than 1 x 10 ¹ Pa ^ if not more than 1 x 10 ³ Pa ^ s, and a proportion (12/11) of the viscosity of fusion meets the following Formula (1):
-0.8 <(1/2) log10 (12/11) <-0.1 (1).
[14]
14. Multilayer structure, according to claim
1, characterized by the fact that a ratio (i ^ b / iW of a melt viscosity (ι 2B) of the layer B resin composition to a melt viscosity (| 2a) of the layer A resin composition, as determined at a temperature of 210 ° C and a shear rate of 1,000 / sec, it is 0.3 or more and 2 or less.
[15]
15. Multilayer structure according to claim 1, characterized by the fact that a temperature higher than a Vicat softening temperature of the resin composition that constitutes layer A or layer B by 30 ° C, the composition of the resin layer A and / or layer B has a melting viscosity (11 '), as determined at a shear rate of 10 / sec, not less than 1 x 10 ² Pa if not more than 1 x 10 ⁴ Pa if viscosity of melting (12 '), as determined at a shear rate of 1,000 / sec being not less than 1 x 10 Pa if not more than 1 x 10 ³ Pa s, and
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6/6 where a proportion (η2 '/ ηι') of the melting viscosity satisfies the following Formula (1 '):
-0.8 <(1/2) log (η2 '/ ^') <-0.1 (1 ').
[16]
16. Multilayer structure according to claim 1, characterized by the fact that at a temperature higher than the Vicat softening temperature of the layer A resin composition by 30 ° C, a ratio (n2B / γ | 2α ) of a melt viscosity (n2B ') of the layer B resin composition to a melt viscosity (η2Α) of the layer A resin composition, as determined at a shear rate of 1,000 / sec, is 3 or more and 3 or less.
[17]
17. Multilayer structure according to claim 1, characterized by the fact that a bonding reaction occurs at an interface between layer A and layer B.
[18]
18. Multilayer structure, according to claim 1, characterized by the fact that it is suitable for food packaging.
[19]
19. Method for producing a multilayer structure, as defined in any one of claims 1 to 18, characterized by the fact that it comprises coextruding:
(i) a resin composition comprising a resin barrier, and (ii) a resin composition comprising a thermoplastic resin.

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同族专利:

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公开号 | 公开日

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CN102712182A|2012-10-03|

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BR112012013271A2|2016-03-01|

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RU2555016C2|2015-07-10|

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EP2508343A1|2012-10-10|

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US20120237747A1|2012-09-20|

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CN102712182B|2015-09-02|

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CA2782339C|2018-05-22|

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EP2508343B1|2020-03-11|

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JPWO2011068105A1|2013-04-18|

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RU2012127324A|2014-01-10|

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US9186873B2|2015-11-17|

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JP5702733B2|2015-04-15|

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CA2782339A1|2011-06-09|

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WO2011068105A1|2011-06-09|

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EP2508343A4|2013-05-22|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2835659A|1957-02-11|1958-05-20|Eastman Kodak Co|Polypropylene waxes and method of making|

---

US3087922A|1958-05-13|1963-04-30|Phillips Petroleum Co|Method and apparatus for pyrolyzing polymers|

---

US3579416A|1966-12-19|1971-05-18|Dow Chemical Co|Packaging film comprising polyolefin outer layers and plural inner gas barrier layers|

---

JPS5044281A|1973-08-23|1975-04-21|

---

DE3021273C2|1979-06-12|1993-03-25|Mitsubishi Petrochemical Co., Ltd., Tokio/Tokyo, Jp|

---

JPH0444561B2|1984-12-26|1992-07-22|Mitsubishi Gas Chemical Co|

---

DE3862580D1|1987-12-23|1991-05-29|Alma Sa|MULTILAYER PLASTIC FILM.|

---

US5089353A|1988-10-14|1992-02-18|Kuraray Co., Ltd.|Multi-layer material having gas barrier properties|

---

DE4030399A1|1990-09-26|1992-04-02|Basf Ag|Polymers and oligomers of propylene¨ with functional end-gps. - produced by reacting hetero-atom. cpds. with corresp. polymers or oligomers contg. unsatd.-olefinic end-gps.|

---

EP0736375B1|1991-03-20|2001-10-04|Kuraray Co., Ltd.|A method for producing a multi-layer construction film|

---

US5178702A|1991-04-04|1993-01-12|The Goodyear Tire & Rubber Company|Pneumatic tire having a multilayered innerliner|

---

EP0646064B1|1993-04-09|1999-06-16|Viskase Corporation|A cheese package, film, bag and process for packaging a co2 respiring foodstuff|

---

US6388007B1|1996-11-19|2002-05-14|Kuraray Co., Ltd.|Resin composition and multilayered structure|

---

US6174949B1|1997-07-25|2001-01-16|Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha|Resin composition, process for preparing the same, and laminate containing layer of said resin composition|

---

EP1109468B1|1998-09-11|2006-11-02|Nike International Ltd|Flexible membranes|

---

JP2000318079A|1999-05-10|2000-11-21|Teijin Ltd|Multilayered stretched film and stretched polyethylene-2,6-naphthalate film|

---

BR0014748A|1999-10-15|2002-07-02|3M Innovative Properties Co|Multilayer films|

---

US7229518B1|2000-11-02|2007-06-12|Nike, Inc.|Process for improving interfacial adhesion in a laminate|

---

US6884483B2|2002-04-30|2005-04-26|Kuraray Co., Ltd.|Multilayer blow molded container|

---

JP4509963B2|2001-05-14|2010-07-21|株式会社クラレ|Process for producing modified ethylene-vinyl alcohol copolymer|

---

CN1231501C|2001-05-14|2005-12-14|可乐丽股份有限公司|Modified ethylene vinyl alcohol copolymer and method for the production thereof|

---

JP2006188710A|2001-05-14|2006-07-20|Kuraray Co Ltd|Method for producing modified ethylene-vinyl alcohol copolymer|

---

JP3851218B2|2001-05-14|2006-11-29|株式会社クラレ|Gas barrier material comprising a modified ethylene-vinyl alcohol copolymer|

---

EP1419903B1|2002-11-13|2008-05-28|Bridgestone Corporation|Innerliner for pneumatic tires and pneumatic tire|

---

US20080003390A1|2005-04-27|2008-01-03|Nahoto Hayashi|Multi-Layer Structure and Process for Production Thereof|

---

JP2006272569A|2005-03-28|2006-10-12|Kuraray Co Ltd|Multilayer film and flexible container using the film|

---

WO2007037541A1|2005-09-30|2007-04-05|The Yokohama Rubber Co., Ltd.|Poorly air-permeable rubber laminate composed of poorly air-permeable resin and rubber composition, and method for production thereof|

---

WO2007083785A1|2006-01-17|2007-07-26|The Yokohama Rubber Co., Ltd.|Low-permeable rubber laminate and pneumatic tire using same|

---

WO2007129371A1|2006-04-25|2007-11-15|The Nippon Synthetic Chemical Industry Co., Ltd.|Multilayer film|

---

JP4990575B2|2006-07-24|2012-08-01|株式会社ブリヂストン|Inner liner for pneumatic tire and pneumatic tire provided with the same|

---

EP2517900B1|2006-07-24|2014-04-23|Bridgestone Corporation|Laminated body and method of producing the same as well as innerliner for pneumatic tire and pneumatic tire|

---

JP2008213840A|2007-02-28|2008-09-18|Kuraray Co Ltd|Oxygen-absorbing packaging material and package|

---

JP2009220793A|2008-03-18|2009-10-01|Bridgestone Corp|Tire|

---

JP5226356B2|2008-03-31|2013-07-03|株式会社クラレ|Ethylene-vinyl alcohol copolymer resin composition|

---

JP5592616B2|2008-03-31|2014-09-17|株式会社ブリヂストン|Film, inner liner for tire, and tire using the same|CN101600764A|2007-01-18|2009-12-09|横滨橡胶株式会社|Have the Amilan polyamide resin composition of excellent ductility and flexing fatigue and pneumatic tyre and the flexible pipe that uses said composition|

---

BR112012024735B1|2010-03-30|2020-03-10|Bekaert Advanced Cords Aalter Nv|Splice by splicing a first tape to a second tape, both tapes comprising parallel steel strands and tape comprising said seam|

---

CA2794706C|2010-03-31|2018-05-22|Kuraray Co., Ltd.|Multilayered structure and laminate, and method for production of the same|

---

JP5583223B2|2010-10-01|2014-09-03|株式会社クラレ|Multilayer structure, inner liner and pneumatic tire using the same|

---

US20120097685A1|2010-10-25|2012-04-26|Vladislav Babinsky|Insulated Beverage Container|

---

JP5802400B2|2011-02-14|2015-10-28|日東電工株式会社|Resin sheet for sealing, semiconductor device using the same, and method for manufacturing the semiconductor device|

---

GB201102803D0|2011-02-17|2011-04-06|Ind Textiles & Plastics Ltd|Chemical resistant ground membrane|

---

JP5784369B2|2011-05-31|2015-09-24|株式会社ブリヂストン|Multilayer structure, inner liner for pneumatic tire, and pneumatic tire|

---

US8986823B1|2011-07-20|2015-03-24|Bryce Corporation|Microlayer extrusion coating and laminating for flexible packaging|

---

DE102011084523A1|2011-10-14|2013-04-18|Evonik Industries Ag|Use of a multi-layer film with Sauerstoffpermeationssperre for the production of photovoltaic modules|

---

JP5948800B2|2011-11-10|2016-07-06|株式会社リコー|Reversible thermosensitive recording medium and reversible thermosensitive recording member|

---

JP2013111822A|2011-11-28|2013-06-10|Sumitomo Bakelite Co Ltd|Multilayer film and package|

---

KR20150053773A|2012-09-07|2015-05-18|미츠비시 가스 가가쿠 가부시키가이샤|Oxygen-absorbing resin composition and oxygen-absorbing multilayer body using same|

---

EP2932536A4|2012-12-14|2016-08-10|Sun Chemical Corp|Compositiions and methods for improved solar cells|

---

JP6103924B2|2012-12-25|2017-03-29|株式会社クラレ|Adhesive laminate|

---

WO2014122941A1|2013-02-08|2014-08-14|株式会社クラレ|Product provided with packaging material containing multilayer structure|

---

JP6494596B2|2014-03-19|2019-04-03|積水化学工業株式会社|Sheet laminated lithium ion secondary battery and method for producing sheet laminated lithium ion secondary battery|

---

EP2960053A1|2014-06-24|2015-12-30|Inergy Automotive Systems Research |Plastic liner for a composite pressure vessel|

---

US9650548B2|2014-08-06|2017-05-16|Equistar Chemicals, Lp|Polyolefin-based compositions, adhesives, and related multi-layered structures prepared therefrom|

---

SG11201702684XA|2014-11-20|2017-05-30|Asahi Glass Co Ltd|Mold release film, process for its production, and process for producing semiconductor package|

---

US20180093458A1|2015-04-03|2018-04-05|Toyo Seikan Group Holdings, Ltd.|Multilayered container|

---

JP2018529794A|2015-07-31|2018-10-11|ダウ グローバル テクノロジーズ エルエルシー|Aminobenzoate-terminated materials for laminating adhesives|

---

JP6724019B2|2015-09-18|2020-07-15|株式会社クラレ|Resin composition, method for producing the same, and multilayer structure|

---

JP6791155B2|2015-10-09|2020-11-25|三菱瓦斯化学株式会社|Manufacturing method of medical multi-layer container and medical multi-layer container|

---

EP3369762B1|2015-10-28|2021-03-03|Mitsubishi Chemical Corporation|Saponified ethylene-vinyl ester-based copolymer pellet, and its manufacturing method|

---

CN110662814B|2017-05-15|2021-11-16|陶氏环球技术有限责任公司|Water-based adhesive composition|

---

CN111148789A|2017-11-22|2020-05-12|三菱化学株式会社|Resin composition, material for melt molding, multilayer structure, and material for liquid packaging|

---

CN108131632A|2017-12-13|2018-06-08|柏涛涛|A kind of intelligent solar street light|

---

US11130319B2|2017-12-29|2021-09-28|Kuraray Co., Ltd.|Multilayer article suitable for use as a fumigation barrier|

---

JP2021104579A|2018-04-06|2021-07-26|株式会社クラレ|Geomembrane, and landfill sheet and radon barrier film using the same|

---

DE112020003088T5|2019-06-26|2022-03-10|Kuraray Co., Ltd.|RESIN COMPOSITION AND MULTI-LAYER STRUCTURE AND PACKAGING MATERIAL USING THESE|

---

WO2021060308A1|2019-09-24|2021-04-01|株式会社クラレ|Laminate|

---

WO2021060309A1|2019-09-24|2021-04-01|株式会社クラレ|Multi-layer structure, molded article, and method for producing molded article|

---

CN111454668A|2020-04-13|2020-07-28|杭州福斯特应用材料股份有限公司|Co-extrusion adhesive film, solar cell module and double-layer glass|

法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2019-04-24| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

---

2019-07-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2019-09-17| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/11/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/11/2010, OBSERVADAS AS CONDICOES LEGAIS |

优先权:

---

申请号 | 申请日 | 专利标题

---

JP2009-273838|2009-12-01|

---

JP2009273838|2009-12-01|

---

JP2010-005369|2010-01-13|

---

JP2010005369|2010-01-13|

---

JP2010005367|2010-01-13|

---

JP2010-005367|2010-01-13|

---

JP2010224362|2010-10-01|

---

JP2010-224362|2010-10-01|

---

PCT/JP2010/071415|WO2011068105A1|2009-12-01|2010-11-30|Multilayer structure and method for producing same|

---