Resin composition and multilayered container

专利摘要:
The present invention provides a resin composition having an oxygen scavenging function. This resin composition contains a gas barrier resin (A), thermoplastic resins (B) other than the said gas barrier resin (A), and a compatibilizer (C), and the oxygen permeation rate of the said gas barrier resin (A) Is 500 ml · 20 μm / m 2 · day · atm (20 ° C., 65% RH) or less, the thermoplastic resin (B) has a carbon-carbon double bond, and the oxygen absorption rate of the resin composition is 0.001 ml / m 2. more than day
公开号:KR20020047313A
申请号:KR1020027005559
申请日:2001-08-31
公开日:2002-06-21
发明作者:다이신지；시모히로유키；나카야마사카즈；이케다가오루
申请人:나카무라 하사오；가부시키가이샤 구라레；
IPC主号:

专利说明:

Resin composition and multilayered container
[2] A gas barrier resin, for example, an ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as EVOH) and the like can be melt-molded and is excellent in oxygen or carbon dioxide gas barrier properties. For this reason, for example, a layer made of EVOH and a layer of a thermoplastic resin (for example, thermoplastic polyester; hereinafter sometimes referred to as PES) having excellent moisture resistance and mechanical properties are included. The multilayer structure is used for various molded objects (for example, a film, a sheet, a bottle, a container, etc.) which require gas barrier property. For example, such a multilayer structure is used in various fields as a multilayer container, especially in the form of bags, bottles, cups, pouches, and the like. For example, it is widely used in the fields of food, cosmetics, medical chemicals, cosmetics and the like.
[3] The above multilayer container has excellent barrier properties such as oxygen and carbonic acid gas, but the permeability of gas such as oxygen is not always close to zero, such as metal materials used in canning, glass used in bottles, and the like. It penetrates innumerable amounts of gas. In particular, in containers such as foods, there is a fear of deterioration in quality due to oxidation of the contents in the case of long-term storage, and therefore, there is a strong demand for improvement of oxygen barrier properties.
[4] On the other hand, when filling the contents, oxygen may be mixed in the container at the same time as the contents. When the contents are easy to oxidize, there is a possibility that the contents of the contents may be deteriorated even by this trace amount of oxygen. In order to prevent this, it is proposed to impart an oxygen scavenging function to the material of the container. In this case, since oxygen to be infiltrated from the outside of the container is also eliminated, the gas barrier property of the packaging material is also improved.
[5] For example, as a method of imparting an oxygen scavenging function to the gas barrier resin constituting the material of the container, (1) by adding an oxidation catalyst such as a transition metal to EVOH, the EVOH is easily oxidized to impart an oxygen scavenging function. (Japanese Unexamined Patent Application Publication No. 4-211444); (2) a method of adding polyvinyl chloride to a polyvinyl chloride to render polyvinyl chloride susceptible to oxidation and to impart an oxygen scavenging function (Japanese Patent Application Laid-Open No. 4-45144); (3) a method of dispersing a resin composition composed of a polyolefin and an oxidation catalyst, that is, a polyolefin in an easily oxidized state in EVOH to impart an oxygen scavenging function to EVOH (Japanese Patent Laid-Open No. 5-156095); (4) JP-A-5-170980 is known to mix EVOH, a polyolefin, and an oxidation catalyst, and to give the oxygen scavenging function by bringing the EVOH and the polyolefin into an easily oxidized state. However, the above-mentioned methods of (1) and (2) do not have sufficient effects of improving oxygen barrier properties, and (3) and (4) have a problem that the transparency of the gas barrier resin is significantly impaired.
[6] In the above multilayer container, in particular, when the adhesive resin layer is not provided between the layers, a thermoplastic resin layer (for example, a PES layer) is provided when the container is subjected to an impact such as filling and dropping a beverage or food. It is easy to produce delamination between the EVOH layer and the EVOH layer, which is a major problem in appearance.
[1] The present invention relates to a resin composition having an oxygen scavenging function. In addition to the oxygen scavenging function, the present invention also relates to a resin composition having excellent gas barrier properties, moisture resistance, steering properties, and flavor barrier properties, and a multilayer container using the resin composition.
[53] 1 is a graph showing the oxygen absorption amount of the first single layer film of Example 1 with respect to time.
[54] 2 is a graph showing the oxygen absorption amount of the monolayer films of Examples 1 to 4 and Comparative Examples 1 to 4 with respect to time. However, Example 1 is a result of a 2nd single layer film.
[55] 3 is a graph showing the oxygen permeation rate of the multilayer films of Examples 1 to 4 and Comparative Examples 1 to 4 with respect to time.
[56] 4 is a graph showing the oxygen absorption amount of the single layer films of Examples 5 to 7, and Comparative Examples 5 and 6 with respect to time.
[57] FIG. 5 is a graph showing the oxygen permeation rate of Example 5 and the multilayer films of Comparative Examples 5 and 6 against time. FIG.
[58] EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail.
[59] In the present specification, "exhaust" oxygen means absorbing and consuming oxygen in a given environment or reducing the amount thereof.
[60] [Gas barrier resin (A)]
[61] The kind of gas barrier resin (A) contained in the 1st resin composition and 2nd resin composition of this invention is not specifically limited, Any resin can be used as long as it is resin which has favorable gas barrier property. Specifically, a resin having an oxygen permeation rate of 500 ml · 20 μm / m 2 · day · atm (20 ° C., 65% RH) or less is used. This means that when measured in an environment of 20 ° C and 65% RH, the volume of oxygen that permeates an area of 1 m 2 and 20 μm thick per day in a state where there is a pressure difference of 1 atmosphere of oxygen is 500 ml or less. it means. When oxygen permeation rate exceeds 500 ml * 20 micrometer / m <2> * day * atm, the gas barrier property of the resin composition obtained will become inadequate. The oxygen permeation rate of the gas barrier resin (A) is preferably 100 ml · 20 μm / m 2 · day · atm or less, more preferably 20 ml · 20 μm / m 2 · day · atm or less, and more preferably 5 ml · It is 20 micrometers / m <2> * day * atm or less.
[62] The refractive index of the gas barrier resin (A) is preferably in the range of 1.50 to 1.56. If it is out of this range, as mentioned later, the difference between the refractive index of gas barrier resin (A) and the refractive index of thermoplastic resin (B) becomes large, and there exists a possibility that transparency of the resin composition obtained may fall. Generally, since the refractive index of the thermoplastic resin (B) having oxygen absorptivity is often in the above range, it becomes easy to reduce the difference in the refractive index between the thermoplastic resin (B) and the gas barrier resin (A). As a result, a resin composition having good transparency can be obtained. The refractive index of the gas barrier resin (A) is more preferably 1.51 or more, and still more preferably 1.52 or more. More preferably, it is 1.55 or less, More preferably, it is 1.54 or less.
[63] Examples of the gas barrier resin (A) as described above include polyvinyl alcohol-based resins, polyamide resins, polyvinyl chloride resins, polyacrylonitrile resins, and the like, but are not limited to these resins.
[64] Among the gas barrier resins (A), polyvinyl alcohol-based resins are homopolymers of vinyl esters or copolymers of vinyl esters with other monomers (particularly copolymers of vinyl esters and ethylene) using alkali catalysts. Obtained by saponification. Although vinyl acetate is mentioned as a typical compound as vinyl ester, Other fatty acid vinyl ester (vinyl propionate, vinyl pivalate, etc.) can also be used.
[65] The degree of saponification of the vinyl ester component of the polyvinyl alcohol-based resin is suitably 90% or more, more preferably 95% or more, and still more preferably 96% or more. If the saponification degree is less than 90 mol%, gas barrier property under high humidity will fall. In addition, when the polyvinyl alcohol-based resin is EVOH, thermal stability becomes insufficient, and gel butt is generated, which is likely to be contained in a molded article.
[66] When a polyvinyl alcohol-type resin consists of a mixture of 2 or more types of polyvinyl alcohol-type resins from which a degree of saponification differs, the average value computed from a mixing weight ratio is made into saponification degree.
[67] Among the above-described polyvinyl alcohol-based resins, EVOH is suitable because melt molding is possible and gas barrier properties under high humidity are good.
[68] It is preferable that the ethylene content of EVOH is 5-60 mol%. If the ethylene content is less than 5 mol%, the gas barrier properties under high humidity may be lowered, and the melt moldability may also be deteriorated. The ethylene content of EVOH is suitably 10 mol% or more, more preferably 15 mol% or more, and optimally 20 mol% or more. On the other hand, when ethylene content exceeds 60 mol%, sufficient gas barrier property may not be obtained. Ethylene content is suitably 55 mol% or less, More preferably, it is 50 mol% or less.
[69] EVOH suitably used has an ethylene content of 5 to 60 mol% and a saponification degree of 90% or more as described above. In the multilayer container containing the resin composition of the present invention, when it is desired to have excellent impact peel resistance, the ethylene content is 25 mol% or more and 55 mol% or less, and the saponification degree is 90% or more and less than 99% EVOH is used. It is preferable.
[70] When EVOH consists of a mixture of two or more types of EVOHs having different ethylene contents, the average value calculated from the mixed weight ratio is taken as the ethylene content. In this case, it is preferable that the difference in the ethylene content between EVOHs having the largest ethylene content is 30 mol% or less, and the difference in the degree of saponification is 10% or less. When deviating from these conditions, transparency of the resin composition layer may be impaired. The difference in ethylene content is more suitably 20 mol% or less, and more suitably 15 mol% or less. The difference in degree of encapsulation is more preferably 7% or less, more preferably 5% or less. In the multilayer container comprising the resin composition of the present invention, when it is desired to balance the impact peel resistance and the gas barrier property to a higher level, the ethylene content is 25 mol% or more and 55 mol% or less, and the degree of saponification is 90% or more to less than 99% of EVOH (a1), ethylene content of 25 mol% to 55 mol%, saponification degree of 99% or more of EVOH (a2), the blending weight ratio a1 / a2 of 5/95 to It is preferable to mix and use so that it becomes 95/5.
[71] The ethylene content and saponification degree of EVOH can be obtained by nuclear magnetic resonance (NMR) method.
[72] As mentioned above, this EVOH can contain a small amount of monomers other than ethylene and vinyl alcohol as a copolymerization component in the range in which the objective of this invention is not impaired. Examples of such monomers include the following compounds: α-olefins such as propylene, 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene; Unsaturated carboxylic acids such as itaconic acid, methacrylic acid, acrylic acid, maleic anhydride, salts thereof, partial or complete esters thereof, nitriles thereof, amides thereof, anhydrides thereof; Vinylsilane-based compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxyethoxy) silane and methacryloxypropyltrimethoxysilane; Unsaturated sulfonic acids or salts thereof; Alkyl thiols; Vinylpyrrolidones and the like.
[73] Among these, when EVOH contains 0.0002 to 0.2 mol% of a vinylsilane compound as a copolymerization component, the composition of the present invention containing the EVOH is co-extruded together with the resin (for example, PES) which should be the base material. At the time of molding or extrusion molding to obtain a multilayer structure, the consistency of melt viscosity with the base resin is improved, and homogeneous moldings can be produced. As a vinylsilane type compound, vinyl trimethoxysilane and vinyl triethoxysilane are used suitably.
[74] Moreover, even when the boron compound is added to EVOH, the melt viscosity of EVOH is improved, and it is effective at obtaining a homogeneous coextrusion or a projected molding. Examples of the boron compound include boric acids, boric acid esters, borates, boron hydrides, and the like. Specifically, examples of the boric acid include orthoboric acid (hereinafter sometimes abbreviated as boric acid), metaboric acid, tetraboric acid, and the like, and examples of the boric acid esters include triethyl borate and trimethyl borate. Alkali metal salts, alkaline earth metal salts, borax, etc. of said various boric acids are mentioned. Among these compounds, orthoboric acid is preferred.
[75] When the boron compound is added, its content is suitably 20 to 2000 ppm, more preferably 50 to 1000 ppm in terms of element boron. By being in this range, EVOH in which torque fluctuations during heating and melting are suppressed can be obtained. If it is less than 20 ppm, the addition effect of a boron compound may become inadequate. On the other hand, when it exceeds 2000 ppm, it becomes easy to gelatinize and may become moldability defect.
[76] It is also effective to add 5 to 5000 ppm of alkali metal salt in terms of alkali metal element to EVOH for improvement of interlayer adhesion and compatibility. The addition amount of the alkali metal salt is more preferably 20 to 1000 ppm, more preferably 30 to 500 ppm in terms of alkali metal elements. Examples of the alkali metal include lithium, sodium, potassium, and the like, and examples of the alkali metal salt include aliphatic carboxylates, aromatic carboxylates, phosphates, and metal complexes of alkali metals. For example, sodium acetate, potassium acetate, sodium phosphate, lithium phosphate, sodium stearate, potassium stearate, sodium salt of ethylenediamine tetraacetic acid, etc. are mentioned, Among these, sodium acetate, potassium acetate, and sodium phosphate are suitable. .
[77] It is also preferable to add a phosphoric acid compound with respect to EVOH suitably in the ratio of 20-500 ppm, more suitably 30-300 ppm, and optimally 50-200 ppm in conversion of a phosphate group. By mix | blending a phosphoric acid compound in the said range, the thermal stability of EVOH can be improved. In particular, it is possible to suppress the occurrence and coloring of the gel-like butt when performing melt molding for a long time.
[78] The kind of phosphorus compound added to EVOH is not specifically limited, Various acids, such as phosphoric acid and phosphorous acid, its salt, etc. can be used. The phosphate may be any of the first phosphate, the second phosphate, and the third phosphate. Although the kind of cation of a phosphate is not specifically limited, It is preferable that a kind of cation is an alkali metal or alkaline-earth metal. Among these, it is preferable to add a phosphorus compound in the form of sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate.
[79] A suitable melt flow rate (MFR) of EVOH (210 ° C., at 2160 g load, based on JIS K7210) is 0.1 to 100 g / 10 minutes, more suitably 0.5 to 50 g / 10 minutes, more preferably 1 to 30 g / 10. Minutes.
[80] The kind of polyamide resin is not specifically limited in gas barrier resin (A), For example, polycaproamide (nylon-6), poly undecanamide (nylon-11), polylaurolactam (nylon- 12) aliphatic polyamide homopolymers such as polyhexamethyleneadipamide (nylon-6,6) and polyhexamethylene sebacamide (nylon-6,12); Caprolactam / laurolactam copolymer (nylon-6 / 12), caprolactam / aminoundecanoic acid copolymer (nylon-6 / 11), caprolactam / ω-aminononanoic acid copolymer (nylon-6 / 9), Caprolactam / hexamethyleneadipamide copolymer (nylon-6 / 6,6), caprolactam / hexamethyleneadipamide / hexamethylene sebacamide copolymer (nylon-6 / 6,6 / 6,12) Aliphatic polyamide copolymers; Aromatic polyamides, such as polymethaxylylene adipamide (MX-nylon) and hexamethylene terephthalamide / hexamethylene isophthalamide copolymer (nylon-6T / 6I), are mentioned. These polyamide resins may be used alone or in combination of two or more thereof. Among these, polycaproamide (nylon-6) and polyhexamethyleneadipamide (nylon-6,6) are suitable from the viewpoint of gas barrier properties.
[81] As polyvinyl chloride resin, besides the homopolymer of vinyl chloride or vinylidene chloride, the copolymer with vinyl acetate, a maleic acid derivative, higher alkyl vinyl ether, etc. are mentioned.
[82] As polyacrylonitrile resin, the copolymer with acrylic acid ester etc. is mentioned besides the homopolymer of acrylonitrile.
[83] As the gas barrier resin (A), one of these may be used, or two or more thereof may be mixed and used. Among these, polyvinyl alcohol-type resin is preferable, and EVOH of 5 to 60 mol% of ethylene content and 90% or more of saponification degree is more preferable. When the gas barrier resin (A) is such EVOH and the compatibilizer (C) described later has a carboxyl group, the thermal stability of the resulting resin composition is remarkably improved.
[84] In the present invention, heat stabilizers, ultraviolet absorbers, antioxidants, colorants, fillers, and other resins (polyamides, polyolefins, etc.) may be previously added to the gas barrier resin (A) within a range not impairing the object of the present invention. Can be.
[85] [Thermoplastic resin (B)]
[86] The thermoplastic resin (B) contained in the resin composition of this invention contains a carbon-carbon double bond. Since the carbon-carbon double bond reacts efficiently with oxygen, this thermoplastic resin (B) has an oxygen scavenging function. In addition, in this invention, a carbon-carbon double bond includes a conjugated double bond, but does not include the multiple bond contained in an aromatic ring.
[87] In the 1st resin composition and 2nd resin composition of this invention, if it is resin which has the said characteristic as a kind of thermoplastic resin (B), and resin other than said gas barrier resin (A), it will not specifically limit. In addition, in the 3rd resin composition and 4th resin composition of this invention, the kind of thermoplastic resin (B) will not be specifically limited if it is resin which has the said characteristic.
[88] In the third resin composition and the fourth resin composition of the present invention, such a carbon-carbon double bond is required to be contained in the thermoplastic resin (B) at least 0.0001 eq / g (equivalent amount / g), and suitably 0.0005 eq / g or more, more preferably 0.001 eq / g or more. When the content of the carbon-carbon double bond is less than 0.0001 eq / g, the oxygen scavenging function of the resulting resin composition is insufficient. Moreover, also in the 1st resin composition and 2nd resin composition of this invention, it is preferable that content of a carbon-carbon double bond is more than the said numerical value.
[89] The carbon-carbon double bond may be included in the main chain of the thermoplastic resin (B) or may be included in the side chain, but the larger the amount of the double bond included in the side chain (that is, the group having a carbon-carbon double bond). Is more preferable from the viewpoint of the efficiency of the reaction with oxygen. As the carbon-carbon double bond included in the side chain, a double bond included in the structural unit represented by the following formula (I) is preferable:
[90] Formula I
[91]
[92] In Formula I,
[93] R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
[94] R ₂ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group,
[95] R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group which may be substituted, -COOR ₅ , -OCOR ₆ , a cyano group or a halogen atom,
[96] R ₅ and R ₆ are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group.
[97] The carbon number of the aryl group is preferably 6 to 10, the carbon number of the alkylaryl group and the arylalkyl group is preferably 7 to 11, and the carbon number of the alkoxy group is preferably 1 to 10. As an example of an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, an aryl group is an phenyl group, an alkylaryl group is an tolyl group, an arylalkyl group is an benzyl group, an alkoxy group is an methoxy group, an ethoxy group, an example of a halogen atom A chlorine atom is mentioned each.
[98] Among the structural units represented by the formula (I), structural units derived from diene compounds are preferred. It is because manufacture of the thermoplastic resin which has the said structure is easy. Examples of such diene compounds include isoprene, butadiene, 2-ethylbutadiene, 2-butylbutadiene, and the like. Only 1 type of these may be used and 2 or more types may be used together. Table 1 shows a relationship between an example of a diene compound and a kind of group represented by the formula (I) derived from the diene compound.
[99] R ₁ R ₂ R ₃ R ₄Isoprene CH ₃ H HCH ₃ HH HH butadiene H H H H 2-ethylbutadiene C ₂ H ₅ H HC ₂ H ₅ HH HH 2-butylbutadiene C ₄ H ₉ H HC ₄ H ₉ HH HH
[100] Among these, it is preferable that R <_2> is a C1-C5 alkyl group from a viewpoint of the efficiency of reaction with oxygen, and it is more preferable that R <_2> is a methyl group (that is, a structural unit derived from isoprene). Since isoprene is easy to obtain and copolymerization with another monomer is also possible, it is suitable also from the viewpoint of the manufacturing cost of a thermoplastic resin (B). Moreover, butadiene is also preferable from a viewpoint that it is easy to obtain and copolymerization with another monomer is possible.
[101] When the structural unit represented by general formula (I) is derived from a diene compound, it is preferable that the ratio of the structural unit represented by general formula (I) with respect to all the structural units derived from a diene compound is 10% or more, 20% or more is more preferable, More preferably 30% or more. In order to make the said ratio 10% or more, the method generally used in the said field which employs an anionic polymerization of a diene compound using a Lewis base as a cocatalyst in an inert organic solvent is employ | adopted.
[102] In order to obtain the thermoplastic resin (B) which has a structural unit represented by General formula (I), when polymerizing the monomer containing a diene compound, it is preferable to use a Lewis base as a cocatalyst. Examples of the Lewis base include ethers such as dimethyl ether, diethyl ether, methyl ethyl ether and tetrahydrofuran, glycol ethers such as ethylene glycol diethyl ether and ethylene glycol dimethyl ether, N, N, N ', N Tertiary amines such as' -tetramethylethylenediamine (TMEDA) and triethylenediamine, and ether-containing amines such as N-methylmorpholine and N-ethylmorpholine. These Lewis bases are usually used in an amount of 0.1 to 400 parts by weight per 100 parts by weight of the initiator described later.
[103] It is preferable that the thermoplastic resin (B) used for the resin composition of this invention is a copolymer of an aromatic vinyl compound and the said diene compound. When a thermoplastic resin (B) is the said copolymer, since the carbon-carbon double bond part derived from a diene compound becomes easy to react with oxygen, the oxygen barrier property and oxygen scavenging function of the resin composition obtained improve. Moreover, the melting behavior and hardness of a thermoplastic resin (B) can be controlled by adjusting the copolymerization ratio of an aromatic vinyl compound and a diene compound. Moreover, the refractive index of a thermoplastic resin (B) can be made into a desired value by adjusting the said copolymerization ratio. Therefore, the difference between the refractive index of gas barrier resin (A) and the refractive index of thermoplastic resin (B) can be made small, and as a result, the product excellent in transparency is obtained.
[104] As said aromatic vinyl compound, styrene, 1-vinyl naphthalene, 2-vinyl naphthalene, 3-vinyl naphthalene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexyl styrene, 4 -Dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene, etc. are mentioned. Among them, styrene is most preferable from the viewpoint of production cost and ease of polymerization. In addition, as a diene compound, said compound is mentioned as an example.
[105] As a form of the copolymer of an aromatic vinyl compound and a diene compound, any form, such as a random copolymer, a block copolymer, a graft copolymer, or these composites, may be sufficient. It is preferable that it is a block copolymer from a viewpoint of the ease of manufacture, the mechanical characteristic of the thermoplastic resin (B) obtained, the ease of handling, and an oxygen scavenging function.
[106] In the block copolymer, the molecular weight of the aromatic vinyl compound block is preferably 300 to 100000, more preferably 1000 to 50000, and still more preferably 3000 to 50000. When the molecular weight of an aromatic vinyl compound block is less than 300, since the melt viscosity of a thermoplastic resin (B) becomes low, a problem may arise in the moldability, workability, and handleability of the resin composition obtained. Moreover, the mechanical characteristic at the time of using a molded object may fall. In addition, the dispersibility of the thermoplastic resin (B) to the gas barrier resin (A) may decrease, and the transparency, the gas barrier property, and the oxygen scavenging function may decrease. On the other hand, when the molecular weight of an aromatic vinyl compound block exceeds 100000, since the melt viscosity of a thermoplastic resin (B) becomes high and a thermoplastic is damaged, the moldability and workability of the resin composition obtained may fall. Moreover, the dispersibility to the gas barrier resin (A) of a thermoplastic resin (B) falls as mentioned above, and transparency, gas barrier property, and oxygen scavenging function may fall.
[107] As a block form of a block copolymer, X (YX) _n , (XY) _n, etc. are mentioned, for example. Here, X is an aromatic vinyl compound block, Y represents a diene compound block, and n is an integer of 1 or more. Among these, a binary block copolymer and a ternary block copolymer are preferable, and a ternary block copolymer is more preferable from a mechanical characteristic viewpoint. Of these, the aromatic vinyl compound block is a polystyrene block, and the diene compound block is a polyisoprene block, which is suitable in view of production cost and ease of polymerization.
[108] Although the manufacturing method of the said block copolymer is not specifically limited, Anion polymerization method is suitable. Specifically, a method of copolymerizing an aromatic vinyl compound and a diene compound using an alkyllithium compound as an initiator and coupling with a coupling agent, a method of sequentially polymerizing a diene compound and an aromatic vinyl compound using a dilithium compound as an initiator Although it is mentioned, it is not limited to these. As the alkyl lithium compound, an alkyl lithium compound having 1 to 10 carbon atoms of an alkyl group, for example, methyl lithium, ethyl lithium, benzyl lithium, n-butyl lithium, secondary-butyl lithium, tert-butyl lithium, or the like is preferable. .
[109] As the coupling agent, dichloromethane, dibromomethane, dichloroethane, dibromoethane and the like are used. As a dilithium compound, naphthalenedilithium, oligostyryldilithium, dirithiohexylbenzene, etc. are mentioned, for example. As for the usage-amount, 0.01-0.2 weight part of initiators and 0.04-0.8 weight part of coupling agents are suitable with respect to 100 weight part of all monomers used for superposition | polymerization.
[110] The thermoplastic resin (B) may have a functional group containing a hetero atom. In particular, in the first resin composition and the second resin composition of the present invention, when the structure of the entire resin composition is stabilized and a multilayer container having a layer made of the resin composition is produced, the multilayer structure in the container. Since the impact resistance peelability of can be improved, it is suitable. The manufacturing method of the thermoplastic resin (B) which has a functional group containing a hetero atom is not specifically limited. Examples thereof include a method of reacting a polymer containing an alkali metal at one or more terminals with a specific terminal treatment agent capable of reacting with the alkali metal at the terminal.
[111] Examples of the functional group containing a hetero atom which may be contained in the thermoplastic resin (B) include the following groups.
[112] [I] active hydrogen-containing polar groups
[113] -SO ₃ H, -SO ₂ H, -SOH, -NH ₂ , -NHR,> C = NH, -CONH ₂ , -CONHR, -CONH-, -OH, -SH
[114] [II] polar groups containing nitrogen and free of active hydrogen
[115] -NR ₂ , -NR-,> C = N-, -CN, -NCO, -OCN, -SCN, -NO, -NO ₂ , -NCS, -CONR ₂ , -CONR-
[116] [III] Polar Groups Containing Epoxy or Thioepoxy Groups
[117] [IV] Carbonyl group or thiocarbonyl group-containing polar group
[118] -CHO, -COOH, -COOR, -COR,> C = O,> C = S, -CHS, -CSOR, -CSOH
[119] [V] phosphorus-containing polar group
[120] -P (OR) ₂ , -P (SR) ₂ , -PO (OR) ₂ , -PO (SR) ₂ , -PS (OR) ₂ , -PS (SR) ₂ , -PO (SR) (OR) , -PS (SR) (OR)
[121] [VI] M (M is any of Si, Ge, Sn, Pb) -containing polar group
[122] _{-MX 3, -MX 2 R, -MXR} 2, -MR 3 ( In the above general formula, R is an alkyl group, a phenyl group or an alkoxy group, X represents a halogen atom.)
[123] As a solvent for manufacturing a thermoplastic resin (B), the organic solvent inert with respect to the said initiator, a coupling agent, and a Lewis base is used. Among these, saturated hydrocarbons having 6 to 12 carbon atoms, cyclic saturated hydrocarbons and aromatic hydrocarbons are preferable. For example, hexane, heptane, octane, decane, cyclohexane, toluene, benzene, xylene, etc. are mentioned. The polymerization reaction for producing the thermoplastic resin (B) is usually carried out at a temperature range of -20 to 80 ° C for 1 to 50 hours.
[124] For example, the polymerization reaction solution is added dropwise to a poor solvent such as methanol, and after the reaction product is precipitated, the reaction product is heated or dried under reduced pressure, or the polymerization reaction solution is added dropwise to boiling water, and the solvent is azeotropically removed. By heating or drying under reduced pressure, a thermoplastic resin (B) is obtained. In addition, the part of the double bond which exists after superposition | polymerization may be reduced with hydrogen in the range which does not impair the effect of the resin composition of this invention.
[125] It is preferable that the main dispersion peak temperature of tan-delta derived from the diene compound block of the block copolymer obtained in this way is -40 degreeC-60 degreeC from a viewpoint of the oxygen scavenging function of the resin composition obtained, -20 degreeC-40 degreeC Is more preferable, and -10 degreeC-30 degreeC are still more preferable. When the main dispersion peak temperature of tan-delta is less than -40 degreeC, the oxygen scavenging function of the resin composition obtained may fall. On the other hand, when the main dispersion peak temperature of tan-delta exceeds 60 degreeC, the oxygen scavenging function in especially low temperature of the resin composition obtained may fall.
[126] The molecular weight of the thermoplastic resin (B) is suitably 1000-50000, More preferably, it is 10000-250000, More preferably, it is the range of 40000-200000. When the molecular weight of a thermoplastic resin (B) is less than 1000, dispersibility to gas barrier resin (A) may fall, and transparency, gas barrier property, and oxygen scavenging function may fall. When molecular weight exceeds 500000, the workability of a resin composition may worsen in addition to the same problem. The thermoplastic resin (B) may be a single number or a mixture composed of a plurality of resins. In either case, when it is desired to obtain a molded article having good transparency, it is preferable that the internal haze value is 10% or less in a film having a thickness of 20 μm.
[127] In the 1st resin composition and 2nd resin composition of this invention, it is preferable that the difference of the refractive index of the thermoplastic resin (B) used for this invention, and the refractive index of gas barrier resin (A) is 0.01 or less. When the difference in refractive index between the gas barrier resin (A) and the thermoplastic resin (B) exceeds 0.01, the transparency of the resulting resin composition may deteriorate. The difference in refractive index is more preferably 0.007 or less, and still more preferably 0.005 or less. However, when a gas barrier resin (A) consists of two or more types of gas barrier resins (for example, when it consists of two other types of EVOH), it calculates from the refractive index and weight ratio of each gas barrier resin. The average value of the refractive index is taken as the refractive index of the gas barrier resin (A).
[128] The thermoplastic resin (B) may contain antioxidant. As antioxidant, the following compound is mentioned, for example. 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-p-cresol, 4,4'-thiobis (6-tert-butylphenol), 2, 2'- Methylenebis (4-methyl-6-tert-butylphenol), octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 4,4' -Thiobis- (6-tert-butylphenol), tert-butyl-6- (tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, pentaerythritol Tetrakis (3-laurylthiopropionate), 2,6-di- (tert-butyl) -4-methylphenol (BHT), 2, 2-methylenebis- (6-tert-butyl-p -Cresol), triphenyl phosphite, tris phosphite (nonylphenyl), dilauryl thiodipropionate and the like.
[129] The addition amount of antioxidant is suitably determined in consideration of the kind, content, use purpose of a resin composition, storage conditions, etc. of each component in a resin composition. Usually, the amount of the antioxidant contained in the thermoplastic resin (B) is preferably 0.01 to 1% by weight, more preferably 0.02 to 0.5% by weight based on the total weight of the thermoplastic resin (B) and the antioxidant. Do. When the amount of the antioxidant is too large, the reaction between the thermoplastic resin (B) and oxygen is hindered, so that the oxygen barrier property and oxygen scavenging function of the resin composition of the present invention may be insufficient. On the other hand, when the amount of the antioxidant is too small, the reaction with oxygen proceeds at the time of preservation or melt kneading of the thermoplastic resin (B), and the oxygen scavenging function decreases before actual use of the resin composition of the present invention. There is.
[130] For example, when the thermoplastic resin (B) is stored at a relatively low temperature or in an inert gas atmosphere, or melt kneaded in a nitrogen-sealed state to produce a resin composition, the amount of the antioxidant is at least good. Moreover, when adding an oxidation catalyst at the time of melt-mixing in order to accelerate | stimulate oxidation, even if a thermoplastic resin (B) contains some amount of antioxidant, the resin composition which has a favorable oxygen scavenging function can be obtained.
[131] [Compatibilizer (C)]
[132] The compatibilizer (C) contained in the resin composition of this invention is a compound which forms a stable structure in the resin composition obtained by improving the compatibility of gas barrier resin (A) and a thermoplastic resin (B). The kind of compatibilizer (C) is not specifically limited, It selects suitably by the combination of the gas barrier resin (A) and thermoplastic resin (B) to be used.
[133] In the case where the gas barrier resin (A) is a resin having high polarity such as polyvinyl alcohol-based resin, the compatibilizer (C) is preferably a hydrocarbon-based polymer or an ethylene-vinyl alcohol copolymer containing a polar group. For example, in the case of the hydrocarbon polymer containing a polar group, the affinity of the said compatibilizer (C) and a thermoplastic resin (B) becomes favorable by the hydrocarbon polymer part which consists of a polymer base. By a polar group, the affinity of the said compatibilizer (C) and gas barrier resin (A) becomes favorable. As a result, a stable structure can be formed in the resin composition obtained.
[134] As a monomer which forms the hydrocarbon polymer part which consists of a base of the hydrocarbon type polymer containing said polar group, the following compound is mentioned: Ethylene, propylene, 1-butene, isobutene, 3-methylpentene, 1-hexene, 1 Α-olefins such as octene; Styrene, α-methylstyrene, 2-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene Styrenes such as 4- (phenylbutyl) styrene, 2,4,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxy styrene and tert-butoxy styrene; Vinyl naphthalenes, such as 1-vinyl naphthalene and 2-vinyl naphthalene; Vinylene group-containing aromatic compounds such as indene and acenaphthylene; Conjugated diene compounds such as butadiene, isoprene, 2,3-dimethylbutadiene, pentadiene, and hexadiene; The said hydrocarbon type polymer may mainly contain 1 type of these monomers, and may contain 2 or more types mainly.
[135] Using this monomer, as described below, a hydrocarbon-based polymer containing a polar group is prepared, and the monomer forms a hydrocarbon polymer portion composed of the following polymer: polyethylene (ultra low density, low density, linear low density, medium Density, high density), olefin polymers such as ethylene- (meth) acrylic acid ester (methyl ester, ethyl ester, etc.) copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, ethylene-propylene copolymer ; Polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene-diene-based block copolymer (styrene-isoprene-block copolymer, styrene-butadiene copolymer, styrene-isoprene-styrene block copolymer And the like; styrene polymers such as hydrogenated products thereof; (Meth) acrylic acid ester polymers, such as polymethyl acrylate, polyethyl acrylate, and polymethyl methacrylate; Vinyl halide-based polymers such as polyvinyl chloride and vinylidene fluoride; Semiaromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate; Aliphatic polyesters such as polyvalerolactone, polycaprolactone, polyethylene succinate and polybutylene succinate. Among these, it is preferable to contain as a structural component the monomer which comprises a thermoplastic resin (B) in many cases. For example, when the thermoplastic resin (B) contains polystyrene, as the polymer constituting the hydrocarbon polymer portion of the compatibilizer (C), polystyrene, a styrene-diene-based block copolymer (styrene-isoprene-block copolymer, styrene Styrene-based polymers such as butadiene copolymer, styrene-isoprene-styrene block copolymer and the like, and hydrogenated products thereof.
[136] Although it does not specifically limit as a polar group contained in a compatibilizer (C), The functional group containing an oxygen atom is preferable. Specifically, an active hydrogen-containing polar group (-SO ₃ H, -SO ₂ H, -SOH, -CONH ₂ , -CONHR, -CONH-, -OH, etc.), a polar group containing nitrogen and not containing active hydrogen ( -NCO, -OCN, -NO, -NO ₂ , -CONR ₂ , -CONR-, etc., epoxy group, carbonyl group-containing polar group (-CHO, -COOH, -COOR, -COR,> C = O, -CSOR, -CSOH, etc.), phosphorus containing polar groups (-P (OR) ₂ , -PO (OR) ₂ , -PO (SR) ₂ , -PS (OR) ₂ , -PO (SR) (OR), -PS (SR (OR) etc.), a boron containing polar group, etc. are mentioned. (In the said general formula, R represents an alkyl group, a phenyl group, or an alkoxy group.)
[137] The manufacturing method of the hydrocarbon type polymer containing a polar group is not specifically limited. For example, the following method can be mentioned: 1) a method of copolymerizing a monomer capable of forming the hydrocarbon polymer moiety and a monomer containing a polar group (or a group capable of forming the polar group); 2) a method of using an initiator or a chain transfer agent having the polar group (or a group capable of forming the polar group) when polymerizing a monomer capable of forming the hydrocarbon polymer moiety; 3) living polymerization of the monomer capable of forming the hydrocarbon polymer moiety, and using the monomer having the polar group (or the group capable of forming the polar group) as a terminating agent (terminating agent); And 4) polymerizing the monomer capable of forming the above hydrocarbon polymer moiety to obtain a polymer, and forming the polar group (or the polar group) on a reactive part of the polymer, for example, a carbon-carbon double bond moiety. A method of introducing a monomer having a group) by a reaction. In the method of 1) above, any copolymerization method of random copolymerization, block copolymerization or graft copolymerization may be employed.
[138] When the compatibilizer (C) is a hydrocarbon-based polymer, particularly preferred polar groups include carboxyl groups and boron-containing polar groups (boronic acid groups and boron-containing groups which can be converted to boronic acid groups in the presence of water). Hereinafter, these polar groups and hydrocarbon-based polymers containing the polar groups will be described in sequence.
[139] In this specification, a "carboxyl group" includes a carboxylic anhydride group and a carboxylic acid base in addition to a carboxyl group. Of these, the carboxylic acid base refers to the residue of the carboxylic acid in which all or part of the carboxylic acid is present in the form of a metal salt. Examples of the metal of the metal salt include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, transition metals such as zinc, manganese and cobalt. Among these, zinc is preferable from the viewpoint of compatibility. When the hydrocarbon polymer having a carboxyl group is used as the compatibilizer (C), the thermal stability of the resulting resin composition is remarkably improved.
[140] Although the method of preparing the hydrocarbon type polymer containing a carboxyl group is not specifically limited, It is suitable to copolymerize the monomer which can form a hydrocarbon polymer part, and the monomer containing a carboxyl group or a carboxylic anhydride group by the method of said 1). Do. As a monomer which has a carboxyl group among the monomers which can be used for such a method, acrylic acid, methacrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, itaconic acid, etc. are mentioned. Among these, acrylic acid and methacrylic acid are preferable. The content of carboxyl groups in the polymer is preferably 0.5 to 20 mol%, more preferably 2 to 15 mol%, even more preferably 3 to 12 mol%.
[141] Examples of the monomer having a carboxylic acid anhydride group include itaconic anhydride, maleic anhydride, and the like, and maleic anhydride is particularly suitable. As content of the carboxylic anhydride group in a polymer, Preferably it is 0.0001-5 mol%, More preferably, it is 0.0005-3 mol%, More preferably, it is 0.001-1 mol%.
[142] The carboxylic acid base is introduced into the polymer by, for example, a salt exchange reaction between a polymer having a carboxyl group or a carboxylic anhydride group prepared by the above method and a low molecular metal salt. The low molecular metal salt at this time may contain 1 type of said metal, and may contain 2 or more types.
[143] As an ion of the metal in a low molecular metal salt, the anion derived from an organic acid or a chloride is mentioned. Examples of the organic acid include acetic acid, stearic acid, dimethyldithiocarbamic acid, palmitic acid, 2-ethylhexanoic acid, neodecanoic acid, linoleic acid, toluic acid, oleic acid, resinic acid, capric acid, naphthenic acid, and the like. Can be mentioned. Particularly preferred low molecular metal salts include cobalt 2-ethylhexanoate, cobalt neodecanoic acid, cobalt stearate and cobalt acetate.
[144] The degree of neutralization of the obtained carboxylic acid base is suitably less than 100%, more preferably 90% or less, and still more preferably 70% or less. Also preferably 5% or more, more preferably 10% or more, and more preferably 30% or more. For example, it is suitably 5 to 90%, more preferably 10 to 70%.
[145] Although the kind of hydrocarbon-type polymer containing a carboxyl group is not specifically limited, The air obtained by copolymerization with the monomer which has the said carboxyl group or carboxylic anhydride group using alpha-olefin as a monomer which can form a hydrocarbon polymer part is mentioned. Coalescence is preferred. Among these, a random copolymer is preferable from the viewpoint of the thermal stability of the resin composition obtained.
[146] As said random copolymer, an ethylene-acrylic acid copolymer (EAA), an ethylene-methacrylic acid copolymer (EMAA), and these metal salts are mentioned. Among these, EMAA and its metal salt are preferable.
[147] Moreover, the copolymer which grafted the monomer which has said carboxyl group or carboxylic anhydride group to polyolefin is also used suitably. As the polyolefin at this time, polyethylene (for example, high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra low density polyethylene (VLDPE), etc.), polypropylene, copolymerized polypropylene, and ethylene- Vinyl acetate copolymer is mentioned as a suitable thing. As the monomer to be grafted, maleic anhydride is preferable.
[148] The hydrocarbon polymer containing a carboxyl group may contain the following monomer as a copolymerization component: vinyl ester, such as vinyl acetate and vinyl propionate; Unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, isobutyl methacrylate and diethyl maleate; Carbon monoxide and the like.
[149] The melt flow rate (MFR) (190 DEG C, 2160 g load) of the polymer containing the carboxyl group is usually 0.01 g / 10 min or more, preferably 0.05 g / 10 min or more, more preferably 0.1 g / 10 Is more than a minute. The MFR is usually 50 g / 10 min or less, preferably 30 g / 10 min or less, and more preferably 10 g / 10 min or less.
[150] When the polar group contained in the compatibilizer (C) is a boron-containing polar group, as described above, a boronic acid group and a boron-containing group which can be converted into a boronic acid group in the presence of water are suitable. The boronic acid group corresponds to the residue except OH group from boric acid and is represented by the following general formula (II):
[151]
[152] The boron-containing group which can be converted into boronic acid group in the presence of water refers to a boron-containing group which can be converted into boronic acid group represented by the above formula (II) by being hydrolyzed in the presence of water. More specifically, water is used alone, or a mixture of water and an organic solvent (toluene, xylene, acetone, etc.) or a mixture of an aqueous 5% boric acid solution and an organic solvent is used as a solvent, and is used for 10 minutes to 2 minutes under conditions of room temperature to 150 ° C. When time hydrolyzed, it means the functional group which can be converted into boronic acid group. As a representative example of such a functional group, the boronic acid ester group represented by following formula (III), the boronic anhydride group represented by following formula (IV), the boronic acid base represented by following formula (V), etc. are mentioned.
[153]
[154]
[155]
[156] In the above formula,
[157] X ₁ and X ₂ are hydrogen atoms, aliphatic hydrocarbon groups (such as linear or branched alkyl groups having 1 to 20 carbon atoms, or alkenyl groups), alicyclic hydrocarbon groups (cycloalkyl groups, cycloalkenyl groups, etc.), aromatic hydrocarbon groups ( Phenyl group, biphenyl group, etc.), wherein X ₁ and X ₂ may be the same or different. However, X ₁ and X ₂ together are excluded in the case of a hydrogen atom. And X ₁ and X ₂ may be combined],
[158] R ₅ , R ₆ and R ₇ represent a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group such as X ₁ and X _2, and R ₅ , R ₆ and R ₇ may be the same or different,
[159] Mt represents an alkali metal,
[160] X ₁ , X ₂ , R ₅ , R ₆ and R ₇ may have other groups such as carboxyl groups, halogen atoms and the like.
[161] The hydrocarbon-based polymer having the boron-containing polar group shows extremely excellent performance as a compatibilizer. For example, when the multilayer container which consists of a layer which consists of a resin composition containing such a polymer, and a PES layer directly contact is produced, impact peeling resistance improves remarkably.
[162] Specific examples of the boronic acid ester group represented by the formula (III) include the following groups: boronic acid dimethyl ester group, boronic acid diethyl ester group, boronic acid dipropyl ester group, boronic acid diisopropyl ester group, boronic acid dibutyl ester group, Boronic acid dihexyl ester group, boronic acid dicyclohexyl ester group, boronic acid ethylene glycol ester group, boronic acid propylene glycol ester group, boronic acid 1, 3- propanediol ester group, boronic acid 1, 3- butanediol ester group, boronic acid Neopentyl glycol ester group, boronic acid catechol ester group, boronic acid glycerin ester group, boronic acid trimethylol ethane ester group and the like.
[163] Examples of the boronic acid base represented by the general formula (V) include alkali metal bases of boronic acid. Specifically, a sodium boron base, a potassium boron base, etc. are mentioned.
[164] The content of the boron-containing polar group in the thermoplastic resin (B) having the boron-containing polar group as a functional group containing a hetero atom is not particularly limited, but is preferably 0.0001 to 1 meq / g (milliequivalents / g), and 0.001 to 0.1 meq. / g is more preferred.
[165] The manufacturing method of the hydrocarbon type polymer which has the said boron containing polar group is not specifically limited. Any of the methods 1) to 4) can be applied. Representative examples of the methods of 1), 2) and 4) are described below.
[166] By the method (1) (the method of copolymerizing a monomer capable of forming a hydrocarbon polymer portion with a monomer having a polar group or a group capable of forming the polar group), a monomer having a boron-containing polar group, and the hydrocarbon polymer portion By copolymerizing the monomer which can form (olefin type polymer, a vinyl type polymer, a diene type polymer, etc.), the hydrocarbon type polymer which has a boron containing polar group is obtained. As a monomer which has the said boron containing polar group, 3-acryloyl aminobenzene boronic acid, 3-acryloyl aminobenzene boronic acid ethylene glycol ester, 3-methacryloyl aminobenzene boronic acid, 3-metha, for example Cryloyl aminobenzene boronic acid ethylene glycol ester, 4-vinyl phenyl boronic acid, 4-vinyl phenyl boronic acid ethylene glycol ester, etc. are mentioned.
[167] The hydrocarbon-based polymer having a boron-containing polar group is also a monomer (olefin-based polymer, vinyl-based polymer, diene-based monomer) capable of forming a hydrocarbon polymer portion by using a thiol having a boron-containing polar group as a chain transfer agent. Monomers capable of forming a polymer and the like). The obtained polymer has a boron containing polar group at the terminal.
[168] The thiol having a boron-containing polar group (eg boronic acid group) is obtained by, for example, reacting a thiol having a double bond with a diborane or borane complex in a nitrogen atmosphere and then adding alcohols or water. Examples of the thiol having a double bond as a raw material include 2-propene-1-thiol, 2-methyl-2-propene-1-thiol, 3-butene-1-thiol, 4-pentene-1-thiol, and the like. Can be. Among these, 2-propene-1-thiol and 2-methyl-2-propene-1-thiol are preferable. As the borane complex, borane-tetrahydrofuran complex, borane-dimethylsulfide complex, borane-pyridine complex, borane-trimethylamine complex, borane-triethylamine complex and the like are preferable. Among these, borane tetrahydrofuran complex and borane dimethyl sulfide complex are preferable. As for the addition amount of a diborane or a borane complex, an equivalence grade is preferable with respect to the thiol which has a double bond. As reaction temperature, the range of room temperature to 200 degreeC is preferable. As a solvent, Ether solvents, such as tetrahydrofuran (THF) and diglyme; Saturated hydrocarbon solvents, such as hexane, heptane, ethylcyclohexane, and decalin, etc. are mentioned. Among these, THF is preferable. As alcohols added after the reaction, lower alcohols such as methanol and ethanol are preferred, and methanol is more preferred.
[169] As polymerization conditions for obtaining the polymer which has a boron containing polar group at the terminal, an azo- or peroxide-based initiator is used, and the polymerization temperature is preferably in the range of room temperature to 150 ° C. As addition amount of the thiol which has the said boron containing polar group, about 0.001-1 mmol per 1 g of monomers is preferable. Although there is no restriction | limiting in particular as the addition method of the said thiol, When using what is easy to chain transfer, such as vinyl acetate and styrene, as a monomer, it is preferable to add a thiol at the time of superposition | polymerization, and to carry out chain transfer, such as methyl methacrylate, When using a difficult thing, it is preferable to add thiol from the beginning.
[170] As a method of polymerizing a monomer capable of forming the hydrocarbon polymer moiety of the above 4) to obtain a polymer, and introducing a monomer having the polar group (boron-containing polar group) by reaction into the reactive part in the polymer, the following two The method can be mentioned.
[171] The method of 4-1): The hydrocarbon-based polymer having a boron-containing polar group is a thermoplastic resin having a boronic acid dialkyl ester group by reacting a polymer having a carbon-carbon double bond with a borane complex and a boric acid trialkyl ester under a nitrogen atmosphere. After obtaining, it is obtained by making water or alcohol react as needed. In this method, the boron-containing polar group is introduced into the carbon-carbon double bond of the polymer having the carbon-carbon double bond by an addition reaction. In this production method, when a polymer having a double bond at the terminal is used as the raw material, a hydrocarbon polymer having a boron-containing polar group at the terminal is obtained, and when a polymer having a double bond at the side chain or the main chain is used as the raw material, boron is used in the side chain. A hydrocarbon polymer having a containing polar group is obtained.
[172] A normal olefin polymer can be used as a raw material of the said manufacturing method, since it has a double bond at the terminal although it is a little. In addition, as a method of obtaining a polymer having a carbon-carbon double bond, a method of obtaining a olefin polymer having a double bond at the terminal by thermal decomposition of an ordinary olefin polymer under anoxic conditions, and an olefin monomer and a diene polymer as raw materials As a method of obtaining these copolymers, etc. are mentioned.
[173] As a borane complex used for the said reaction, the borane complex described by the method of said 2) is mentioned. Among these, borane-trimethylamine complex and borane triethylamine complex are more preferable. The amount of the borane complex to be added is preferably in the range of 1/3 to 10 mol based on 1 mol of the carbon-carbon double bond of the thermoplastic resin.
[174] As said boric acid trialkyl ester, boric acid lower alkyl esters, such as trimethyl borate, triethyl borate, tripropyl borate, and tributyl borate, are preferable. The amount of boric acid trialkyl ester added is preferably in the range of 1 to 100 mol with respect to 1 mol of carbon-carbon double bonds of the thermoplastic resin. The solvent does not need to be used in particular, but when used, saturated hydrocarbon solvents such as hexane, heptane, octane, decane, dodecane, cyclohexane, ethylcyclohexane and decalin are preferable.
[175] The reaction temperature is usually in the range of room temperature to 300 deg. C, preferably 100 to 250 deg. C, and at this temperature, the reaction is preferably carried out for 1 minute to 10 hours, preferably 5 minutes to 5 hours.
[176] The boronic acid dialkyl ester group introduced into the thermoplastic resin by the above reaction can be hydrolyzed by a method generally used in the art to be a boronic acid group. Or it can be made into arbitrary boronic acid ester groups by transesterifying with alcohol by a conventional method. Furthermore, it can dehydrate-condense by heating and it can be set as boronic anhydride group. Furthermore, it can be made into boronic acid base by reaction with a metal hydroxide or a metal alcoholate by a conventional method.
[177] The conversion reaction of such a boron containing functional group is normally performed using organic solvents, such as toluene, xylene, acetone, and ethyl acetate. As alcohol, Mono alcohol, such as methanol, ethanol, butanol; And polyhydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, neopentyl glycol, glycerin, trimethylol ethane, pentaerythritol, and dipentaerythritol. Examples of the metal hydroxides include hydroxides of alkali metals such as sodium and potassium. Moreover, as said metal alcoholate, the metal alcoholate which consists of the said metal and the said alcohol is mentioned. These things are not limited to what was illustrated. These usage-amount is 1-100 mol with respect to 1 mol of boronic acid dialkyl ester groups normally.
[178] The method of 4-2): The hydrocarbon-based polymer having a boron-containing polar group is also a polymer containing a carboxyl group generally known in the art, m-aminophenylbenzeneboronic acid, m-aminophenylboronic acid ethylene glycol ester Amino group containing boronic acid or amino group containing boronic acid ester, such as these, is obtained by amidation-reacting by a conventional method. In reaction, you may use condensing agents, such as carbodiimide.
[179] As a polymer containing the said carboxyl group, it is a semi-aromatic polyester resin (PET etc.), an aliphatic polyester resin, etc., A polymer which contains a carboxyl group at the terminal; The monomer unit which has carboxyl groups, such as acrylic acid, methacrylic acid, itaconic acid, citraconic acid, fumaric acid, maleic anhydride, in polymers, such as a polyolefin resin, a styrene resin, (meth) acrylic acid ester resin, and a vinyl halide-type resin, Polymers introduced by copolymerization; Although the polymer etc. which introduce | transduced maleic anhydride etc. by addition reaction to the thermoplastic resin containing said olefinic double bond are mentioned, It is not limited to these.
[180] The melt flow rate (MFR) (230 ° C., load 2160 g) of the hydrocarbon-based polymer having a boron-containing polar group is suitably in the range of 0.1 to 100 g / 10 minutes, more preferably in the range of 0.2 to 50 g / 10 minutes. .
[181] As the compatibilizer (C), as described above, an ethylene-vinyl alcohol copolymer may also be used. In particular, when the gas barrier resin (A) is EVOH, the effect as a compatibilizer is sufficiently exhibited. Among them, the ethylene-vinyl alcohol copolymer having an ethylene content of 70 to 99 mol% and a saponification degree of 40% or more is preferable from the viewpoint of improving compatibility. The ethylene content is more suitably 72 to 96 mol%, more suitably 72 to 94 mol%. When ethylene content is not satisfy | filling at 70 mol%, affinity with a thermoplastic resin (B) may fall. Moreover, when ethylene content exceeds 99 mol%, affinity with EVOH may fall. The degree of saponification is more suitably 45% or more. There is no restriction | limiting in particular in the upper limit of saponification degree, The thing of substantially 100% saponification degree can also be used. When saponification degree does not satisfy 40%, affinity with EVOH may fall.
[182] The melt flow rate (MFR) of the ethylene-vinyl alcohol copolymer (210 ° C., load 2160 g) is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more. Moreover, it is suitably 100 g / 10 minutes or less, More preferably, it is 50 g / 10 minutes or less, More preferably, it is 30 g / 10 minutes or less.
[183] The compatibilizer (C) described above may be used alone, or two or more thereof may be mixed and used.
[184] When a multilayer container, such as a bottle comprised from the multilayer body which a layer which consists of the resin composition of this invention containing the said compatibilizer (C), and a PES layer directly contact, is produced by, for example, construction blow-out blow molding, a resin composition Adhesion with PES becomes high, and high impact peelability is obtained. Also in this respect, the significance of the present invention is great.
[185] In addition, when the said compatibilizer (C) has a carboxyl group, the resin composition obtained has high thermal stability. As mentioned later, when the transition metal salt (D) mentioned later is excessively contained in a resin composition, the thermal stability of the said resin composition may fall, but the compatibilizer (C) which has a carboxyl group like a transition metal salt (D) If is contained, the thermal stability of the said resin composition is maintained. Although the reason for such a remarkable effect is not clear, it is thought that it is based on some interaction of the said compatibilizer (C) and the transition metal salt (D) mentioned later.
[186] [Transition Metal Salt (D)]
[187] It is necessary for the 2nd resin composition and 4th resin composition of this invention to contain a transition metal salt (D). It is preferable that the 1st resin composition and 3rd resin composition of this invention contain the transition metal salt (D). The transition metal salt (D) has the effect of improving the oxygen scavenging function of the resin composition by promoting the oxidation reaction of the thermoplastic resin (B). For example, it promotes the reaction between the oxygen present in the packaging material obtained from the resin composition of the present invention and the oxygen to be permeated in the packaging material and the thermoplastic resin (B), and improves the oxygen barrier property and oxygen scavenging function of the packaging material. Improve.
[188] In the first resin composition and the second resin composition of the present invention, the transition metal salt (D) is suitably contained in a proportion of 1 to 5000 ppm in terms of metal elements. That is, the transition metal salt (D) is contained in the ratio of 1 to 5000 parts by weight in terms of metal elements with respect to the total amount of 1 million parts by weight of the gas barrier resin (A), the thermoplastic resin (B) and the compatibilizer (C). More suitably, the transition metal salt (D) is contained in the range of 5 to 1000 ppm, more preferably 10 to 500 ppm. When the content of the transition metal salt (D) is not satisfied at 1 ppm, the effect of its addition may be insufficient. On the other hand, when the content of the transition metal salt (D) exceeds 5000 ppm, the thermal stability of the resin composition decreases, and generation of decomposition gas and generation of gel butt may be remarkable.
[189] On the other hand, in the third resin composition and the fourth resin composition of the present invention, the transition metal salt is preferably 1 to 1 in terms of metal elements based on the total amount of the thermoplastic resin (B) and the compatibilizer (C). It is contained at a rate of 50000 ppm. More suitably, the transition metal salt (D) is contained in the range of 5 to 10000 ppm, more preferably 10 to 5000 ppm. When the content of the transition metal salt (D) is not satisfied at 1 ppm, the effect of the addition may be insufficient. On the other hand, when content of a transition metal salt (D) exceeds 50000 ppm, the thermal stability of a resin composition may fall and generation | occurrence | production of a decomposition gas and generation of a gel butt may become remarkable.
[190] Examples of the transition metal used for the transition metal salt (D) include iron, nickel, copper, manganese, cobalt, rhodium, titanium, chromium, vanadium and ruthenium, but are not limited thereto. Among these, iron, nickel, copper, manganese and cobalt are preferable, manganese and cobalt are more preferable, and cobalt is still more preferable.
[191] As an ion of the metal contained in a transition metal salt (D), the anion derived from an organic acid or a chloride is mentioned. Examples of the organic acid include acetic acid, stearic acid, acetylacetone, dimethyldithiocarbamic acid, palmitic acid, 2-ethyl hexanoic acid, neodecanoic acid, linoleic acid, toluic acid, oleic acid, resinic acid, capric acid, naphthenic acid, and the like. Although it is possible, it is not limited to these. Particularly preferred salts include cobalt 2-ethylhexanoate, cobalt neodecanoic acid, and cobalt stearate. In addition, a metal salt has a polymeric diion, so-called ionomer may be sufficient.
[192] [Resin composition]
[193] In the first resin composition and the second resin composition of the present invention, the gas barrier resin (A) is 40 to 99.8 wt%, the thermoplastic resin (B) is 0.1 to 30 wt%, and the compatibilizer (C) is 0.1 to It is preferable to contain 30 weight%. When the content ratio of the gas barrier resin (A) is less than 40% by weight, the transparency in molded products such as a multilayer container using the resin composition is poor, and there is a fear that the gas barrier property against oxygen gas, carbon dioxide gas, etc. may decrease. have. On the other hand, when the content ratio is more than 99.8% by weight, the content ratio of the thermoplastic resin (B) and the compatibilizer (C) decreases, so that the oxygen barrier property and the oxygen scavenging function are lowered. There is a fear that the stability is impaired. The content rate of the gas barrier resin (A) is suitably 60 to 99% by weight, more preferably 80 to 98% by weight, still more preferably 85 to 97% by weight.
[194] The content rate of the said thermoplastic resin (B) becomes like this. More preferably, it is 1-20 weight%, More preferably, it is 2-15 weight%. The content ratio of the compatibilizer (C) is more preferably 0.5 to 20% by weight, still more preferably 1.0 to 10% by weight.
[195] In the 3rd resin composition and 4th resin composition of this invention, it is preferable that 1 to 99 weight% of thermoplastic resins (B) and 1 to 99 weight% of compatibilizers (C) are contained. The content ratio of the thermoplastic resin (B) is more preferably 5 to 95% by weight, still more preferably 30 to 90% by weight, and most preferably 50 to 90% by weight. The content ratio of the compatibilizer (C) is more preferably 5 to 95% by weight, still more preferably 10 to 70% by weight, and most preferably 10 to 50% by weight.
[196] As for the oxygen absorption rate of the 1st resin composition of this invention, it is required to be 0.001 ml / m <2> * day or more, 0.01 ml / m <2> * day or more is preferable, and 0.05 ml / m <2> * day or more is more preferable. When oxygen absorption rate is less than 0.001 ml / m <2> * day, there exists a possibility that the oxygen barrier property and oxygen scavenging effect of the molded object which consists of obtained resin composition may become inadequate. Moreover, it is preferable that the oxygen absorption rate of the 2nd resin composition of this invention is more than said numerical value, too.
[197] Moreover, the oxygen absorption rate of the 3rd resin composition of this invention needs to be 0.1 ml / m <2> * day or more, 0.5 ml / m <2> * day or more is preferable, 1 ml / m <2> * day or more is more preferable, 10 ml / m <2> * day or more is more preferable. Moreover, it is preferable that the oxygen absorption rate of the 4th resin composition of this invention is more than said numerical value, too. The oxygen absorption rate is the volume of oxygen absorbed by the film in unit time per unit surface area when the film of the resin composition is left in a constant volume of air. About a specific measuring method, it shows in the Example mentioned later.
[198] The first resin composition and the second resin composition of the present invention are thermoplastic resins (E) other than the gas barrier resin (A), the thermoplastic resin (B) and the compatibilizer (C) to the extent that the effects of the present invention are not impaired. ) May be contained. Moreover, even if the 3rd resin composition and 4th resin composition of this invention do not impair the effect of this invention, even if it contains thermoplastic resin (E) other than a thermoplastic resin (B) and a compatibilizer (C), good. The thermoplastic resin (E) is not particularly limited, and examples thereof include the following compounds: polyethylene, polypropylene, ethylene-propylene copolymer, ethylene or propylene copolymer (ethylene or propylene and at least one of the following monomers). Copolymer with: alpha -olefins such as 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene, unsaturated carboxylic acids such as itaconic acid, methacrylic acid, acrylic acid, maleic anhydride, Salts thereof, partial or complete esters thereof, nitriles thereof, amides thereof, anhydrides thereof; vinyl formate, vinyl acetate, vinyl propionate, vinylbutyrate, vinyloctanoate, vinyldodecanoate, vinylstearate, vinyl arachidonate and the like Carboxylic acid vinyl esters, vinylsilane-based compounds such as vinyltrimethoxysilane, unsaturated sulfonic acid and salts thereof, alkylthiols, vinylpyrrolidone and the like), poly4-methyl-1- Ten poly polyolefin such as 1-butene; Polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; Polystyrene, polycarbonate, polyacrylate, and the like.
[199] When selecting the thermoplastic resin (E) contained in the resin composition of this invention, it is preferable to consider the miscibility of the said thermoplastic resin (E), a gas barrier resin (A), and a thermoplastic resin (B). The miscibility of these resins may affect gas barrier properties, cleanliness, effectiveness as an oxygen scavenger, mechanical properties, product structure, and the like of the obtained product.
[200] You may make the resin composition of this invention contain various additives in the range in which the effect of this invention is not impaired. Examples of such additives include antioxidants, plasticizers, thermal stabilizers (melt stabilizers), photoinitiators, deodorants, ultraviolet absorbers, antistatic agents, lubricants, colorants, fillers, desiccants, fillers, pigments, dyes, processing aids, flame retardants, antifogging agents (防). Viii) and other high molecular compounds. Among these, (i) thermal stabilizer, (ii) photoinitiator, and (iii) deodorant are demonstrated below.
[201] In the said additive, 1 type (s) or 2 or more types of the metal salt of a hydrotalcite compound and a higher aliphatic carboxylic acid is used as a heat stabilizer of (i). These compounds can prevent generation of a gel or fisheye at the time of preparation of a resin composition, and can further improve long-term operation stability. It is preferable that these compounds are contained in the ratio of 0.01-1 weight% of the whole resin composition.
[202] The metal salt of a higher aliphatic carboxylic acid is a metal salt of a C8-C22 higher fatty acid. Examples of the higher fatty acid having 8 to 22 carbon atoms include lauric acid, stearic acid and myristic acid. Examples of the metal constituting the salt include sodium, potassium, magnesium, calcium, zinc, barium and aluminum. Among them, alkaline earth metals such as magnesium, calcium and barium are suitable. Among the metal salts of such higher aliphatic carboxylic acids, calcium stearate and magnesium stearate are preferable.
[203] The photoinitiator of (ii) is used in the said additive in order to start or accelerate oxygen scavenging in the molded object, packaging film, multilayer structure, etc. which consist of the resin composition of this invention. In particular, when a resin composition contains antioxidant, it is preferable to contain a photoinitiator simultaneously. By irradiating the resin composition containing the photoinitiator with light at a desired time, the initiation of the reaction between the thermoplastic resin (B) and oxygen is promoted, and the induction group for oxygen scavenging of the resin composition is reduced or lost, and as a result, It is possible to express the oxygen scavenging function quickly. Here, an induction group is time until the resin composition of this invention fully starts to capture | acquire oxygen.
[204] Examples of the photoinitiator include, but are not limited to, the following compounds: benzophenone, o-methoxybenzophenone, acetophenone, o-methoxyacetophenone, acenaphthequinone, methylethylketone, valerophenone, hexano Phenone, α-phenylbutyrophenone, p-morpholinopropiophenone, dibenzosveron, 4-morpholinobenzophenone, benzoin, benzoin methyl ether, 4-o-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone, α-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthone, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indanon, 1,3,5-triacetylbenzene, thioxanthene-9-one, xanthene-9-one, 7-H-benz [de] anthracene- 7-one, benzointetrahydropyranylether, 4,4'-bis (dimethylamino) -benzophenone, 1'-acetonaphtone, 2'-acetonaphtone, 2,3-butanedione, benz [a ] Anthracene-7,12-dione, 2, 2-dime -2-phenyl acetophenone, α, α- diethoxyacetophenone, α, α- dibutoxy acetophenone and the like. In addition to these compounds, for example, singlet oxygen generating photosensitizers such as rose bengal, methylene blue, tetraphenylporphyrin, poly (ethylene-carbon monoxide) and oligo [2-hydroxy-2-methyl-1- [4- Polymer initiators, such as (1-methylvinyl) -phenyl] -propane], can also be used as a photoinitiator.
[205] The amount of the photoinitiator to be used is the kind of the thermoplastic resin (B) to be used, the wavelength and intensity of the light to be used, the nature and amount of the antioxidant to be used, the kind of the photoinitiator to be used, or the use of the resin composition of the present invention. It may be appropriately selected depending on the form of. For example, when the molded article which consists of the resin composition of this invention is a little opaque, a comparatively large amount of photoinitiator is needed. Generally, it is suitable that the usage-amount of a photoinitiator is 0.01 to 10 weight% of the whole resin composition.
[206] As the light to be irradiated, for example, ultraviolet or visible light having a wavelength of about 200 to 750 nanometers (nm), preferably about 200 to 400 nm is useful. Since these light have a relatively long wavelength, it is preferable from a viewpoint of manufacturing cost, influence on a human body, etc. As an irradiation amount of light, it is preferable that it is 0.1 joules (J) or more per 1 g of thermoplastic resins (B) contained in the resin composition of this invention, and it is the range of 10-100J normally. In addition to the above light, electron beams, ionizing radiations such as gamma rays, X-rays and corona discharges having a radiation dose of about 0.2 to 20 megarads (Mrad), preferably about 1 to 10 Mrads, can be used. The irradiation of light is preferably performed in the presence of oxygen. The irradiation time of light may be appropriately selected depending on the amount and type of photoinitiator, the shape (thickness, etc.) of the molded product, the amount of antioxidant, the wavelength and intensity of light, and the like.
[207] The timing of the irradiation of the light is not particularly limited as long as it is before the time point when the oxygen scavenging function of the resin composition of the present invention is required. For example, when using the resin composition of this invention as a packaging material, light irradiation may be just before packaging, during packaging, or after packaging. It is preferable to irradiate a resin composition as a flat sheet form from a viewpoint of irradiating light uniformly.
[208] Among the additives, a deodorant (or deodorant, adsorbent; hereinafter referred to as deodorant) is used to reduce odor caused by low molecular by-products generated by oxygen scavenging of the resin composition of the present invention.
[209] There is no restriction | limiting in particular as a kind of deodorant of said (iii), The composition containing a zinc compound, an aluminum compound, a silicon compound, an iron (II) compound, a zinc compound, and a silicon compound, the composition containing a zinc compound, and an aluminum compound, an organic acid And iron (II) compound-organic acid compositions. These may be used independently and may be a mixture of multiple types or double salts.
[210] Examples of the zinc compound include zinc silicate, zinc oxide, zinc sulfate, zinc chloride, zinc phosphate, zinc nitrate, zinc carbonate, zinc acetate, zinc oxalate, zinc citrate, zinc fumarate, and zinc formate.
[211] As an aluminum compound, aluminum sulfate, aluminum phosphate, aluminum silicate, potassium aluminum sulfate, etc. are mentioned.
[212] Examples of the silicon compound include silicon phosphate compounds such as silicon dioxide, silicon orthophosphate, silicon pyrophosphate-I type, and silicon pyrophosphate-II type, and activated silica gel.
[213] The iron (II) compound is not particularly limited as long as it forms a divalent iron ion, and examples thereof include iron (II) sulfate, iron chloride (II), iron nitrate (II), iron bromide (II), and iron iodide ( Inorganic salts such as II), and organic salts such as iron gallate (II), iron malate (II), and iron fumarate (II). Among these, iron (II) sulfate and iron (II) chloride are preferable.
[214] Compositions (mixtures or double salts) containing zinc compounds and silicon compounds are also suitably used. As a specific example of this composition, the ratio of zinc oxide and silicon dioxide is in the range of 1: 5 to 5: 1 by weight, and most have an amorphous structure. Substantially amorphous microparticles of zinc silicate are preferred. The ratio of zinc oxide and silicon dioxide is preferably in the range of 1: 4 to 4: 1, more preferably in the range of 1: 3 to 3: 1.
[215] Compositions of zinc compounds and aluminum compounds are also suitably used. As a specific example of this composition, a mixture of zinc oxide and / or zinc carbonate and aluminum sulfate and / or potassium aluminum sulfate is preferable, with 1 to 1000 parts by weight of aluminum compound, preferably 30 to 100 parts by weight of zinc compound. It is contained in the ratio of 300 weight part.
[216] As organic acids, a C8 or more organic acid, such as aliphatic monocarboxylic acid, aliphatic polycarboxylic acid, aromatic monocarboxylic acid, and aromatic polycarboxylic acid is preferable, and aromatic polycarboxylic acid is especially preferable. Examples of the aromatic polycarboxylic acid are phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, benzenehexacarboxylic acid, naphthalenedicarboxylic acid, naphthalene tree Carboxylic acid, naphthalene tetracarboxylic acid, diphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, azobenzene tetracarboxylic acid, anhydrides thereof, and the like. Among these, benzene tricarboxylic acid, especially trimellitic acid, is preferable.
[217] As an iron (II) compound used for an iron (II) compound-organic acid composition, the compound which melt | dissolves in water as mentioned above and forms bivalent iron ion can be used. The organic acid is not particularly limited as long as it is soluble in water, and for example, ascorbic acid (D- and L-forms), ascorbic acid such as isocorbic acid, metal salts thereof, citric acid, isocitric acid, lactic acid, tartaric acid, malic acid, and the like. Carboxylic acids may be mentioned. Among these, L-ascorbic acid is preferable. At this time, there is no problem even if a mixture of two or more iron (II) compounds and / or two or more organic acids is used.
[218] It is preferable that both iron (II) compound and the organic acid composition couple | bond together. Such a composition can be prepared by, for example, drying the aqueous solution obtained by mixing and dissolving both components by spray drying, freeze drying, or the like to form a powder. The ratio of the iron (II) compound and the organic acid is preferably in the range of 1: 0.01 to 1: 1 by weight, more preferably 1: 0.02 to 1: 0.8. When the organic acid component is ascorbic acid, the ratio of the iron (II) compound and the organic acid is preferably in the range of 1: 0.02 to 1: 0.3 by weight ratio, more preferably 1: 0.02 to 1: 0.13, and 1: 0.05 To 1: 0.13 are more preferred. The iron (II) compound-organic acid composition is preferably added with 2 to 20% by weight of alum as a stabilizer for the deodorizing function based on the total amount of the iron (II) compound and the organic acid. Although there is no restriction | limiting in particular as alum, Kali alum, ammonia alum, sodium alum are suitable.
[219] Other deodorants include compositions stabilized metal compounds consisting of zinc compounds and polycarboxylic acids, bioenzyme model compounds such as iron (II) -phthalocyanine derivatives, paulownia, holly, ash, hairy butterbur, coltsfoot, lilac, artificial forsythia Hydrated magnesium silicate clay minerals, such as aluminosilicates, such as zeolites, aluminosilicates such as zeolites, sepiolites, scirotiles, barigolskates and lapriites, active humic acids Alumina, activated carbon, etc. are used, and a porous adsorbent can also be used.
[220] The content of the deodorant is suitably 0.1% by weight or more, more preferably 0.2 to 50% by weight, and more preferably 0.5 to 10% by weight of the entire resin composition.
[221] A suitable melt flow rate (MFR) of the resin composition of the present invention (based on JIS K7210 at 210 ° C and 2160 g load) is 0.1 to 100 g / 10 minutes, more preferably 0.5 to 50 g / 10 minutes, more preferably 1 To 30 g / 10 min. When the melt flow rate of the resin composition of this invention deviates from the said range, the workability at the time of melt molding often worsens.
[222] In the 1st resin composition and the 2nd resin composition of this invention, it is preferable that the particle | grains which consist of a thermoplastic resin (B) are disperse | distributing in the matrix which consists of a gas barrier resin (A). The molded article made of such a resin composition has good transparency, gas barrier properties and oxygen scavenging function. At this time, it is suitable that the average particle diameter of the particle | grains which consist of a thermoplastic resin (B) is 10 micrometers or less. When the average particle diameter exceeds 10 µm, the area of the interface between the matrix made of the thermoplastic resin (B) and the gas barrier resin (A) or the like becomes small, and the oxygen gas barrier property and the oxygen scavenging function may decrease. . 5 micrometers or less are more preferable, and, as for the average particle diameter of a thermoplastic resin (B) particle | grain, 2 micrometers or less are more preferable.
[223] [Processing of Resin Composition]
[224] Each component of the resin composition of this invention is mixed and processed into a desired product. The method of mixing each component of the resin composition of this invention is not specifically limited. The order at the time of mixing each component is not specifically limited, either. For example, when mixing a gas barrier resin (A), a thermoplastic resin (B), a compatibilizer (C), and a transition metal salt (D), you may mix them simultaneously, and a thermoplastic resin (B) and a compatibilizer ( After mixing C) and transition metal salt (D), you may mix with gas barrier resin (A). Moreover, after mixing a thermoplastic resin (B) and a compatibilizer (C), you may mix with a gas barrier resin (A) and a transition metal salt (D), and a gas barrier resin (A) and a transition metal salt (D) After mixing, you may mix with a thermoplastic resin (B) and a compatibilizer (C). The gas barrier resin (A), the thermoplastic resin (B), and the compatibilizer (C) may be mixed and then mixed with the transition metal salt (D), or the compatibilizer (C) and the transition metal salt (D) may be mixed. After that, the mixture may be mixed with a gas barrier resin (A) and a thermoplastic resin (B). In addition, a mixture obtained by mixing the gas barrier resin (A), the thermoplastic resin (B) and the compatibilizer (C) and the mixture obtained by mixing the gas barrier resin (A) and the transition metal salt (D) may be mixed. good.
[225] As a specific method of mixing, the melt kneading method is preferable in view of the simplicity of the process and the manufacturing cost. At this time, by using a device capable of achieving a high kneading degree, finely and uniformly dispersing each component can improve the oxygen absorption performance and transparency, and can prevent the formation and mixing of gels and butts. It is preferable at the point.
[226] As a high kneading apparatus, a continuous intensive mixer, a kneading type twin screw extruder (in the same direction or different directions), a continuous kneader such as a mixing roll, a kneader, a high speed mixer, a banbury mixer, an intensive mixer, a pressure kneader, or the like A device using a rotating disc having a grinding mechanism such as a stone mortar, such as a type kneader or a KCK kneading extruder manufactured by KCK, a kneading unit (dalmaji, CTM, etc.) installed in a single screw extruder, ribbon blender, brabender Simple kneaders, such as a mixer, etc. are mentioned. Among these, a continuous kneader is preferable. Commercially available continuous intensive mixers include FCM manufactured by Farrel, CIM manufactured by Nihon Seigo Sho, KCM, LCM, ACM manufactured by Kobe Seigo Sho, Ltd., and the like. It is preferable to employ | adopt the apparatus which installs a uniaxial extruder under these kneading machines and performs kneading | mixing and extrusion pelletization simultaneously. As a twin-screw kneading extruder having a kneading disc or a kneading rotor, for example, TEX manufactured by Nihon Seigo Sho, ZSK manufactured by Werner & Pfleiderer, TEM manufactured by Toshiba Kikai Co., Ltd., PCM manufactured by Ikegai Co., Ltd. Can be mentioned.
[227] In these continuous kneaders, the shape of the rotor and the disk plays an important role. In particular, the gap (chip clearance) between the mixing chamber and the rotor chip or the disk chip is important, and a mixture having good dispersibility even if it is too narrow or too wide is not obtained. As chip clearance, 1 to 5 mm is optimal.
[228] The rotation speed of the rotor of a kneader is 100-1200 rpm normally, Preferably it is 150-1000 rpm, More preferably, it is 200-800 rpm. In addition, the kneader chamber inner diameter D is usually 30 mm or more, preferably 50 to 400 mm. Moreover, as for ratio L / D of the chamber length L and the internal diameter D of a kneader, 4-30 are suitable. One kneader may be used and two or more kneaders may be connected and used.
[229] Kneading temperature is the range of 50-300 degreeC normally. In order to prevent oxidation of a thermoplastic resin (B), it is preferable to carry out nitrogen sealing of a hopper opening, and to extrude at low temperature. The longer the kneading time is, the better the result can be obtained. However, from the viewpoint of oxidation prevention and production efficiency of the thermoplastic resin (B), it is usually 10 to 600 seconds, preferably 15 to 200 seconds, more preferably 15 To 150 seconds.
[230] The resin composition of this invention can be shape | molded by various molded objects, for example, a film, a sheet | seat, a container, other packaging materials, etc. by employ | adopting a shaping | molding method suitably. At this time, the resin composition of this invention may be once pelletized, and may be used for shaping | molding, each component of a resin composition may be dry-blended, and may be directly provided for shaping | molding.
[231] As a shaping | molding method and a molded object, it can shape | mold in a hollow container, such as a film | membrane, a sheet | seat, a pipe, etc. by melt-extrusion molding, a container shape by injection molding, and a bottle shape by blow molding. As blow molding, extrusion blow molding in which a Parison is molded by extrusion molding and blow molding is performed, and injection blow molding in which a preform is molded by injection molding and blow molding is preferred.
[232] [Multilayer Structure and Multilayer Container]
[233] In the present invention, the molded article obtained by the above molding may be a single layer, but from the viewpoint of imparting mechanical properties, water vapor barrier properties, further oxygen barrier properties, and the like, it is preferable to use the multilayered product as a multilayer structure. Do.
[234] As a layer structure of a multilayered structure, when a layer which consists of resins other than the resin composition of this invention is x layer, and the resin composition layer of this invention is y layer, and an adhesive resin layer is z layer, x / y, x / y / x, x / z / y, x / z / y / z / x, x / y / x / y / x, x / z / y / z / x / z / y / z / x and the like are illustrated, It is not limited to these. In the case of providing a plurality of x layers, the kind thereof may be the same or different. In addition, the layer using the recovery resin which consists of scraps, such as a trim which generate | occur | produces at the time of shaping | molding, may be provided separately, and a recovery resin may be mix | blended with the layer which consists of another resin. Although the thickness structure of each layer of a multilayer structure is not specifically limited, From a viewpoint of moldability, manufacturing cost, etc., the thickness ratio of the y layer with respect to the whole layer thickness is 2-20%.
[235] As resin used for said x layer, a thermoplastic resin is preferable from a viewpoint of workability. Examples of such thermoplastic resins include, but are not limited to: polyethylene, polypropylene, ethylene-propylene copolymers, ethylene or propylene copolymers (copolymers of ethylene or propylene with at least one of the following monomers): (Alpha) -olefins, such as 1-butene, isobutene, 4-methyl-1- pentene, 1-hexene, and 1-octene; unsaturated carboxylic acids, such as itaconic acid, methacrylic acid, acrylic acid, and maleic anhydride, its salt, its Carboxylic acid vinyl esters, such as partial or complete esters, nitriles thereof, amides thereof, anhydrides thereof; vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyloctanoate, vinyl dodecanoate, vinyl stearate, vinyl arachidonate Vinylsilane-based compounds such as vinyltrimethoxysilane, unsaturated sulfonic acid or salts thereof, alkylthiols, vinylpyrrolidone and the like), poly4-methyl- Polyolefins such as 1-pentene and poly1-butene; Polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; Polyamides such as polyε-caprolactam, polyhexamethyleneadipamide and polymethaxylyleneadipamide; Polyvinylidene chloride, polyvinyl chloride, polystyrene, polyacrylonitrile, polycarbonate, polyacrylate and the like. The thermoplastic resin layer may be non-stretched or may be stretched or rolled uniaxially or biaxially.
[236] Among these thermoplastic resins, polyolefins are preferred from the viewpoints of moisture resistance, mechanical properties, economy, heat sealability, and the like, and polyesters from the viewpoints of mechanical properties, heat resistance and the like.
[237] On the other hand, the adhesive resin used for the z layer is not particularly limited as long as it is capable of adhering the respective layers, and a polyurethane- or polyester-based one-component or two-component curable adhesive, a carboxylic acid-modified polyolefin resin, or the like is suitably used. . The carboxylic acid-modified polyolefin resin may be an olefin polymer or copolymer comprising an unsaturated carboxylic acid or an anhydride thereof (maleic anhydride or the like) as a copolymerization component; Or a graft copolymer obtained by grafting an unsaturated carboxylic acid or an anhydride thereof to an olefinic polymer or copolymer.
[238] Among these, carboxylic acid modified polyolefin resin is more preferable. In particular, when the x layer is a polyolefin resin, the adhesiveness with the y layer becomes good. Examples of such carboxylic acid-modified polyolefin resins include polyethylene (low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra low density polyethylene (VLDPE)), polypropylene, copolymerized polypropylene, ethylene-vinyl acetate copolymer, ethylene- ( The carboxylic acid-modified thing of a meta) acrylic acid ester (methyl ester or ethyl ester) copolymer, etc. are mentioned.
[239] As a method of obtaining a multilayer structure, although the extrusion lamination method, the dry laminated molding method, the construction extrusion molding method, the coextrusion molding method, etc. are illustrated, it is not specifically limited. Examples of the coextrusion molding method include a coextrusion laminate molding method, a coextrusion sheet molding method, a coextrusion inflation molding method, and a coextrusion blow molding method.
[240] The sheet, the film, the parison, and the like of the multilayer structure thus obtained are reheated to a temperature below the melting point of the resin to be contained, and the thermoforming method such as compression molding, the roll stretching method, the fantagraph stretching method, the inflation stretching method, the blow molding method It is also possible to obtain a molded article which is uniaxially or biaxially stretched by stretching or the like.
[241] The resin composition of this invention becomes favorable transparency by selecting suitable resin. Therefore, the packaging container which is easy to visually recognize the contents can be obtained by selecting resin with favorable transparency as another resin to laminate | stack. From such a viewpoint, the haze value of the multilayer structure having the resin composition layer of the present invention is preferably 10% or less, more preferably 5% or less, and even more preferably 3% or less.
[242] The molded article using the multilayer structure is used for various purposes. In particular, the effect of the multilayer structure of the present invention is greatly exerted when a multilayer container is used. Moreover, the multilayer structure which arrange | positioned the layer with high water vapor barrier property on both sides or the high humidity side of the resin composition layer of this invention has especially extended duration of an oxygen scavenging function, and, as a result, has extremely long gas barrier property. It is appropriate in terms of time continuation. On the other hand, the multilayer container which has a resin composition layer in an innermost layer is suitable from a viewpoint that the oxygen scavenging function in a container is exhibited quickly.
[243] Moreover, transparency becomes favorable by the resin composition of this invention selecting a suitable resin. Therefore, such a composition is suitable for the use as a packaging container whose content is easy to see. Among these packaging containers, the following two types of aspects are mentioned as an aspect with the strict performance required for transparency, and the usefulness of using the resin composition of this invention large. That is, one is a container which consists of a layer which consists of a layer which consists of a resin composition of this invention, and the total layer thickness is 300 micrometers or less, and the other is a layer which consists of a resin composition of this invention, and a thermoplastic polyester (PES) layer, respectively. It is a multilayer container containing at least 1 layer. Hereinafter, these embodiments are described sequentially.
[244] The container which consists of a multilayer film which consists of a layer which consists of a resin composition of this invention, and whose total layer thickness is 300 micrometers or less is a flexible container which consists of a multilayer structure with comparatively thin total layer thickness, and is processed in the form of the pouch etc. normally. Since this container has excellent gas barrier property, has a continuous oxygen scavenging function on it, and is easy to manufacture, it is very useful for packaging a product that is susceptible to oxygen and susceptible to deterioration.
[245] Generally as a container which requires favorable transparency, the thickness of each resin layer which comprises a multilayered structure is thin, and the container with thin thickness as a whole is manufactured. For example, when crystalline resins such as polyolefins are used, when the thickness is large, transparency often deteriorates due to scattering due to crystals, whereas good transparency is obtained when the container is thin. In general, resins crystallized by non-stretching have poor transparency, but resins stretched and crystallized have good transparency. Such uniaxially or biaxially stretched films are usually thin, and in this respect, the thin multilayer structure often provides good transparency.
[246] The resin composition of this invention becomes favorable transparency by selecting suitable resin. Therefore, transparency is often required and it can be used suitably for the container which consists of a thin multilayer film. In such a thin film, even if transparency deteriorates with time, the grade is small. Although the thickness of such a multilayer film is not specifically limited, From a viewpoint of maintaining transparency and flexibility, it is suitably 300 micrometers or less, More preferably, it is 250 micrometers or less, More preferably, it is 200 micrometers or less. On the other hand, considering the mechanical properties as a container, the total layer thickness is preferably 10 µm or more, more preferably 20 µm or more, and more preferably 30 µm or more.
[247] When producing said multilayer container from a multilayer film, there is no restriction | limiting in particular in the manufacturing method of the said multilayer film, For example, dry lamination molding, co-extrusion lamination molding, etc. of the resin composition layer and other thermoplastic resin layer of this invention are carried out. By laminating by the method, a multilayer film can be obtained.
[248] In the case of dry lamination, a non-oriented film, a uniaxially oriented film, a biaxially oriented film, a rolled film, or the like can be used. Among these, a biaxially stretched polypropylene film, a biaxially stretched polyethylene terephthalate film, and a biaxially stretched poly (epsilon) -caprolactam film are preferable from a viewpoint of mechanical strength, and a biaxially stretched polypropylene film is especially preferable when moisture resistance is also considered. In the case of using a non-stretched film or a uniaxial stretched film, stretching is performed by reheating the multilayer film after lamination, uniaxially or biaxially stretching by thermoforming methods such as compression molding, roll stretching, fantagraph stretching, inflation stretching, or the like. The obtained multilayer film can also be obtained.
[249] In order to seal the obtained multilayer container, it is also preferable to provide the layer which consists of resin which can be heat-sealed in the at least one outermost layer surface in the manufacturing process of a multilayer film. As such resin, polyolefin, such as polyethylene and a polypropylene, is mentioned.
[250] The multilayer film obtained in this way can be processed into a bag shape, for example, and can be set as the packaging container for filling a content. Since it is flexible and simple, and also excellent in transparency and oxygen scavenging property, it is very useful for the packaging of the content which is easy to deteriorate by presence of oxygen, especially foodstuffs.
[251] The multilayer container including at least one layer of the resin composition of the present invention and at least one layer of the PES layer is excellent in gas barrier properties and oxygen scavenging function, and transparency is good by selecting appropriate resin. For this reason, it is used in various forms, such as a bag-shaped container, a cup-shaped container, and a hollow molded container. Among these, the blow molding container, especially a bottle, is important.
[252] Bottles made of PES are now widely used as beverage containers. In such a use, it is necessary to prevent the deterioration of the contents and to be able to fully recognize the beverage which is the contents. In addition, in the case of filling the contents which are very susceptible to deterioration of flavor by oxygen such as beer, for example, it is required to have extremely high gas barrier properties and oxygen scavenging performance. The multilayer container including at least one layer each of the layer and the PES layer made of the resin composition of the present invention can obtain high transparency and is very suitable for such use because of its excellent retention of quality of contents. As a laminated constitution of a multilayer container, although the adhesive resin layer may be arrange | positioned between a resin composition layer and a PES layer, the multilayer container formed so that a PES layer may directly contact both surfaces of a resin composition layer may have higher transparency. It is especially preferable from a viewpoint which can obtain and fully show the effect of this invention that the impact peeling property between a resin composition layer and a PES layer is excellent.
[253] As PES used for the multilayer container of this invention which consists of a layer which consists of the resin composition of the said invention, and a PES layer, the condensation polymer which uses aromatic dicarboxylic acid or these alkyl esters, and diol as a main component is used. In particular, in order to achieve the object of the present invention, PES mainly containing ethylene terephthalate component is preferable. Specifically, the total ratio (mol%) of the terephthalic acid unit and the ethylene glycol unit is preferably 70 mol% or more, and more preferably 90 mol% or more, based on the total moles of all the structural units constituting the PES. When the total ratio of the terephthalic acid unit and the ethylene glycol unit is less than 70 mol%, the PES obtained becomes amorphous, the mechanical strength is insufficient, and when the contents are heated and filled (hot-filled) after being stretched to a container, the heat shrinkage is large and at the time of use There is a risk of endurance. Moreover, when solid-phase polymerization is performed in order to reduce the oligomer contained in resin, the crosslinking by softening of a resin tends to occur easily, and there exists a possibility that production may become difficult.
[254] The said PES can contain bifunctional compound units other than a terephthalic acid unit and an ethylene glycol unit as needed in the range which does not produce the said problem. As this ratio (mol%), it is preferable that it is 30 mol% or less with respect to the total mole number of all the structural units which comprise PES, 20 mol% or less is more preferable, and 10 mol% or less is still more preferable. As such a bifunctional compound unit, a dicarboxylic acid unit, a diol unit, a hydroxycarboxylic acid unit, etc. are mentioned, Any of aliphatic, alicyclic, and aromatic may be sufficient. Specifically, a neopentyl glycol unit, a cyclohexane dimethanol unit, a cyclohexane dicarboxylic acid unit, an isophthalic acid unit, a naphthalenedicarboxylic acid unit, etc. are mentioned.
[255] Among these, when the obtained PES is used, the isophthalic acid unit has the advantage of having a low defective article rate because of the wide manufacturing conditions for obtaining a good molded product and excellent moldability. It is also preferable at the point which can prevent the whitening of a molded article by suppressing a crystallization rate. Moreover, a 1, 4- cyclohexane dimethanol unit or a 1, 4- cyclohexane dicarboxylic acid unit is preferable at the point that the intensity | strength at the time of the fall of the molded object obtained is further excellent. In addition, the naphthalenedicarboxylic acid unit is preferable because the glass transition temperature of the obtained PES increases, heat resistance is improved, and the ability to absorb ultraviolet rays is imparted, and it is particularly useful when the contents tend to be degraded by ultraviolet rays. . For example, such as beer, it is particularly useful when the contents are easily deteriorated by oxidation or ultraviolet rays.
[256] When using a polycondensation catalyst in manufacture of PES, the catalyst normally used for manufacture of PES can be used. For example, antimony compounds, such as antimony trioxide; Germanium compounds such as germanium dioxide, germanium tetraethoxide and germanium tetra-n-butoxide; Titanium compounds such as tetramethoxytitanium, tetratchicitantan, tetra-n-propoxytitanium, tetraisopropoxytitanium and tetrabutoxytitanium; Tin compounds such as di-n-butyltin dilaurate, di-n-butyltin oxide, dibutyltin diacetate and the like can be used. These catalysts may be used alone or in combination of two or more kinds thereof. As the usage-amount of a polycondensation catalyst, the range of 0.002-0.8 weight% is preferable based on the weight of a dicarboxylic acid component.
[257] Among these, an antimony compound is preferable from a catalyst production cost, and antimony trioxide is especially preferable. On the other hand, a germanium compound is preferable and germanium dioxide is especially preferable at the point that the color tone of PES obtained becomes favorable. Moreover, from a moldability viewpoint, a germanium compound is more preferable than an antimony compound. PES obtained by a polymerization reaction using an antimony compound as a catalyst has a faster crystallization rate than PES polymerized using a germanium compound as a catalyst, and crystallization by heating is likely to proceed during injection molding or blow molding, resulting in Whitening may occur in the bottle, which may impair transparency. Moreover, extending | stretching orientation may fall and a shaping property may deteriorate. Thus, the range of the manufacturing conditions which can obtain a favorable molded object narrows, and there exists a tendency for the defective product rate to rise easily.
[258] In particular, when using a polyethylene terephthalate containing no copolymerization component other than diethylene glycol which occurs incidentally as PES used in the present invention, the germanium compound may be used to suppress the crystallization rate when producing the PES. Preference is given to using as a catalyst.
[259] Although the manufacturing method of the multilayer container of this invention containing at least 1 layer and the layer which consist of the said resin composition, respectively is not specifically limited, It is suitable from a viewpoint of productivity etc. using construction blow molding. In blow-out blow molding, a container is manufactured by extending | stretching blow-molding the container precursor (Parisson) obtained by blow-out molding.
[260] In the injection molding, usually, resins, which must constitute each layer of the multilayer structure, are guided from two or more injection cylinders into concentric nozzles, and are injected into a single mold alternately or at a timing shifted. Molding is performed by performing one mold-fastening operation. For example, (1) First, a PES layer for the inner and outer layers is injected, and then a resin composition to be an intermediate layer is injected to obtain a molding container having a three-layered configuration of PES / resin composition / PES, and (2) for the inner and outer layers. By injection of a PES layer, followed by injection of a resin composition, and at the same time or after this, injection of a PES layer again, and a method of obtaining a molded container having a 5-layered constitution of PES / resin composition / PES / resin composition / PES. Although parison is produced, it is not limited to these manufacturing methods. Moreover, in the said laminated constitution, you may arrange | position an adhesive resin layer between a resin composition layer and a PES layer as needed.
[261] As conditions of injection molding, it is preferable to inject PES in the temperature range of 250-330 degreeC, 270-320 degreeC is more preferable, 280-310 degreeC is still more preferable. When the injection temperature of PES is less than 250 degreeC, PES will not melt enough, a cosmetic melt (fisheye) will be mixed in a molding, and a poor appearance may arise, and at the same time, there exists a possibility of causing the fall of the mechanical strength of a molding. In extreme cases, there is a fear that the screw torque rises and causes a failure of the molding machine. On the other hand, when the injection temperature of PES exceeds 330 degreeC, decomposition | disassembly of PES will become remarkable and there exists a possibility of causing the fall of the mechanical strength of the molding by molecular weight fall. In addition, not only impairing the properties of the substance to be filled in the molded product by gases such as acetaldehyde generated during decomposition, but also resulting in contamination of the mold due to oligomers generated during decomposition may damage the appearance of the molded product.
[262] It is preferable to inject | pour a resin composition in the temperature range of 170-250 degreeC, 180-240 degreeC is more preferable, 190-230 degreeC is still more preferable. When the injection temperature of a resin composition is less than 170 degreeC, a resin composition does not melt enough, but there exists a possibility that cosmetic melt (fisheye) may mix in a molded object, and appearance defect may arise. In extreme cases, there is a fear that the screw torque rises and causes a failure of the molding machine. On the other hand, when the injection temperature of a resin composition exceeds 250 degreeC, oxidation of a thermoplastic resin (B) advances and there exists a possibility that the gas barrier property and oxygen scavenging function of a resin composition may fall. At the same time, poor appearance of the molded product due to coloring or gelling may occur, or fluidity may be uneven or inhibited due to decomposition gas or gelling, resulting in a defective portion of the resin composition layer. In extreme cases, injection molding is impossible due to the generation of gelling. In order to suppress the progress of oxidation during melting, it is also preferable to seal the raw material supply hopper with nitrogen.
[263] In addition, the resin composition may be supplied to the molding machine in the form of pellets in which the raw material components are melt-blended in advance, or may be supplied to the molding machine with each raw material component that has been dry blended.
[264] The temperature of the hot runner portion into which the PES and the resin composition are introduced is preferably in the range of 220 to 300 ° C, more preferably 240 to 280 ° C, and even more preferably 250 to 270 ° C. When the temperature of the hot runner portion is less than 220 ° C., the PES crystallizes and solidifies in the hot runner portion, so that molding may be difficult. On the other hand, when the temperature of the hot runner portion exceeds 300 ° C, oxidation of the thermoplastic resin (B) proceeds, and there is a fear that the gas barrier properties and oxygen scavenging function of the resin composition are deteriorated. At the same time, poor appearance of the molded product due to coloring or gelling may occur, or fluidity may be uneven or inhibited due to decomposition gas or gelling, resulting in a defective portion of the resin composition layer. In extreme cases, injection molding is impossible due to the generation of gelling.
[265] As mold temperature, the range of 0-70 degreeC is preferable, 5-50 degreeC is more preferable, and 10-30 degreeC is still more preferable. Thereby, crystallization of PES and the resin composition of parison are suppressed, uniform elongation is ensured, the interlayer peelability and transparency of the multilayer container obtained are improved, and the stable molded object of shape can be obtained. If the mold temperature is less than 0 ° C., the appearance of the parison is damaged by condensation of the mold, and there is a fear that a good molded product cannot be obtained. In addition, when the mold temperature exceeds 70 ° C, crystallization of the PES and the resin composition of the parison is not suppressed, the stretchability becomes nonuniform, and the interlayer peelability and transparency of the resulting molded product are lowered, It becomes difficult to obtain shaped moldings.
[266] In the Parish obtained in this way, it is preferable that the total thickness is 2-5 mm and the thickness of the resin composition layer is 10-500 micrometers in total.
[267] Said flyson is reheated in a high temperature state directly or using heating elements, such as a block heater and an infrared heater, and is sent to an extending blow process. The multi-layered blow-molded container of the present invention can be produced by stretching heated Parisone 1 to 5 times in the longitudinal direction in the stretching blow step, and then stretching the blow blow 1 to 4 times with compressed air or the like. 75-150 degreeC is preferable, as for the temperature of a parison, 85-140 degreeC is more preferable, 90-130 degreeC is still more preferable, 95-120 degreeC is the most preferable. If the temperature of the parison exceeds 150 ° C, PES tends to crystallize, so the resulting container may be whitened, which may damage the appearance or increase the interlayer peeling of the container. On the other hand, if the temperature of the parison is less than 75 ° C., crazes may occur in the PES, resulting in a pearl bath, and the transparency may be impaired.
[268] The total thickness of the trunk portion of the multilayer container thus obtained is generally 100 to 2000 µm, preferably 150 to 1000 µm, and is used depending on the purpose. It is preferable that it is the range of 2-200 micrometers, and, as for the total thickness of the resin composition layer at this time, 5-100 micrometers is more preferable.
[269] In this way, the multilayer container which consists of a layer which consists of a resin composition of this invention, and a PES layer is obtained. This container is able to obtain high transparency, and is also very excellent in gas barrier properties and oxygen scavenging function. Therefore, it is useful as a container of the contents which are easy to deteriorate by presence of oxygen, for example, food, a medicine. It is especially useful as a container of beverages, such as beer.
[270] Moreover, the resin composition of this invention is suitable also for using as a packing (gasket) for containers, especially as a gasket for the cap of a container. In this case, there is no restriction | limiting in particular as a raw material of a cap main body, The material generally used in the said field | areas, such as a thermoplastic resin and a metal, can be employ | adopted. Since the cap formed by attaching such a gasket is excellent in gas barrier property and has a continuous oxygen scavenging function, it is very useful for packaging a product that is susceptible to oxygen and easily deteriorates.
[7] It is an object of the present invention to provide a composition having an oxygen scavenging function. Another object of the present invention is to provide a resin composition having excellent gas barrier properties, transparency, moisture resistance, steering properties, and flavor barrier properties in addition to the oxygen scavenging function. Moreover, another object of this invention is to provide the multilayer container which is excellent in impact resistance peelability and which is excellent in external appearance, especially transparency containing the layer which consists of the said resin composition.
[8] The first resin composition of the present invention is a resin composition containing a gas barrier resin (A), a thermoplastic resin (B) other than the gas barrier resin (A), and a compatibilizer (C), wherein the gas barrier resin ( The oxygen permeation rate of A) is 500 ml 20 μm / m 2 day atm (20 ° C., 65% RH) or less, and the thermoplastic resin (B) has a carbon-carbon double bond, and the oxygen absorption rate of the resin composition. Is 0.001 ml / m 2 · day or more.
[9] In a suitable embodiment, the first resin composition also contains a transition metal salt (D).
[10] The second resin composition of the present invention is a resin composition containing a gas barrier resin (A), a thermoplastic resin (B) other than the gas barrier resin (A), a compatibilizer (C), and a transition metal salt (D), The oxygen permeation rate of the gas barrier resin (A) is 500 ml · 20 μm / m 2 · day · atm (20 ° C., 65% RH) or less, and the thermoplastic resin (B) has a carbon-carbon double bond.
[11] In a preferred embodiment, the content in the composition of the transition metal salt when the first resin composition contains a transition metal salt (D), and the content in the composition of the transition metal salt (D) contained in the second resin composition are as described above. It is 1 to 5000 ppm in terms of metal elements, based on the total weight of the gas barrier resin (A), the thermoplastic resin (B), and the compatibilizer (C).
[12] In a suitable embodiment, the transition metal salt (D) has at least one transition metal selected from the group consisting of iron, nickel, copper, manganese and cobalt.
[13] In a suitable embodiment, the thermoplastic resin (B) contains a carbon-carbon double bond at a rate of at least 0.0001 eq / g.
[14] In a suitable embodiment, the thermoplastic resin (B) has a unit represented by the following formula (I).
[15]
[16] In Formula I,
[17] R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
[18] R ₂ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group,
[19] R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group which may be substituted, -COOR ₅ , -OCOR ₆ , a cyano group or a halogen atom,
[20] R ₅ and R ₆ are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group.
[21] In a suitable embodiment, the number average molecular weight of the said thermoplastic resin (B) is 1000-50000.
[22] In a suitable embodiment, the gas barrier resin (A) is an ethylene-vinyl alcohol copolymer having an ethylene content of 5 to 60 mol% and a saponification degree of 90% or more.
[23] In a suitable embodiment, the refractive index difference between the gas barrier resin (A) and the thermoplastic resin (B) is 0.01 or less.
[24] In a suitable embodiment, the particles made of the thermoplastic resin (B) are dispersed in the matrix of the gas barrier resin (A).
[25] In a preferred embodiment, the first resin composition and the second resin composition of the present invention, the gas barrier resin (A) in a ratio of 40 to 99.8% by weight, 0.1 to 30% by weight of the thermoplastic resin (B) And the compatibilizer (C) in a proportion of 0.1 to 30% by weight.
[26] The third resin composition of the present invention is a resin composition containing a thermoplastic resin (B) and a compatibilizer (C), wherein the thermoplastic resin (B) has a unit represented by the following general formula (I) and is also a carbon-carbon double The bond is contained in a ratio of 0.0001 eq / g or more, the number average molecular weight of the thermoplastic resin (B) is 1000 to 500000, and the oxygen absorption rate of the resin composition is 0.1 ml / m 2 · day or more.
[27] Formula I
[28]
[29] In Formula I,
[30] R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
[31] R ₂ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group,
[32] R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group which may be substituted, -COOR ₅ , -OCOR ₆ , a cyano group or a halogen atom,
[33] R ₅ and R ₆ are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group.
[34] In a suitable embodiment, the said 3rd resin composition contains a transition metal salt (D).
[35] The fourth resin composition of the present invention is a resin composition containing a thermoplastic resin (B), a compatibilizer (C), and a transition metal salt (D), wherein the thermoplastic resin (B) is a unit represented by the following general formula (I). And a carbon-carbon double bond at a ratio of 0.0001 eq / g or more, and the number average molecular weight of the thermoplastic resin (B) is 1000 to 500000.
[36] Formula I
[37]
[38] In Formula I,
[39] R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
[40] R ₂ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group,
[41] R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group which may be substituted, -COOR ₅ , -OCOR ₆ , a cyano group or a halogen atom,
[42] R ₅ and R ₆ are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group.
[43] In a preferred embodiment, the content in the composition of the transition metal salt when the third resin composition contains the transition metal salt (D), and the content in the composition of the transition metal salt (D) contained in the fourth resin composition are And 1 to 50000 ppm in terms of metal elements based on the total weight of the thermoplastic resin (B) and the compatibilizer (C).
[44] In a suitable embodiment, the said transition metal salt (D) when the said 3rd resin composition contains a transition metal salt (D), and the transition metal salt (D) contained in a 4th resin composition are iron, nickel, At least one transition metal selected from the group consisting of copper, manganese and cobalt.
[45] In a suitable embodiment, the compatibilizer (C) is a thermoplastic resin having at least one functional group selected from the group consisting of carboxyl groups, boronic acid groups, and boron-containing groups which can be converted to boronic acid groups in the presence of water.
[46] In a suitable embodiment, the thermoplastic resin (B) has an aromatic vinyl compound unit and a diene compound unit.
[47] In a suitable embodiment, the diene compound unit is at least one of an isoprene unit and butadiene unit.
[48] In a suitable embodiment, the aromatic vinyl compound unit is a styrene unit.
[49] In a suitable embodiment, the thermoplastic resin (B) is a block copolymer.
[50] The multilayer structure of this invention contains one or more layers which consist of the resin composition of any one of said 1st-4th.
[51] The multilayer container of this invention contains one or more layers, respectively, which consist of the resin composition of any one of said 1st-4th and a thermoplastic polyester layer.
[52] The cap of the present invention is made by attaching a gasket made of any of the first to fourth resin compositions.
[271] Although an Example demonstrates this invention concretely below, this invention is not limited at all by this.
[272] The analysis in this example was performed as follows.
[273] (1) Ethylene Content and Saponification Degree of EVOH:
[274] It was calculated from the spectrum obtained by a deuterated dimethyl sulfoxide as a solvent ¹ H-NMR (nuclear magnetic resonance) measurement (Nihon Denshi claim using "JNM-GX1500 type").
[275] (2) phosphate group content of EVOH:
[276] 10 g of dry chips used as a sample was put into 50 ml of 0.01-mL hydrochloric acid aqueous solution, and it stirred at 95 degreeC for 6 hours. The aqueous solution after stirring was quantitatively analyzed using ion chromatography, and the phosphate group content was obtained as the phosphate ion (PO ₄ ^3- ) content. As the column for chromatography, CIS-A23 manufactured by Yokogawa Denki Co., Ltd. was used, and an aqueous solution containing 2.5 mm of sodium carbonate and 1.0 mm of sodium hydrogencarbonate was used as the eluent. In addition, the calibration curve produced by the phosphoric acid aqueous solution was used for quantification.
[277] (3) Sodium salt, potassium salt and magnesium salt content of EVOH:
[278] 10 g of dry chips used as a sample was put into 50 ml of 0.01-mL hydrochloric acid aqueous solution, and it stirred at 95 degreeC for 6 hours. The aqueous solution after stirring was quantitatively analyzed using ion chromatography, and the sodium salt, potassium salt and magnesium salt contents were obtained in the amounts of metals as respective cation contents. As the column for chromatography, ICS-C25 manufactured by Yokogawa Denki Co., Ltd. was used, and an aqueous solution containing 5.0 mM tartaric acid and 1.0 mM 2,6-pyridinedicarboxylic acid was used as the eluent. In addition, in quantification, the analytical curve created by the aqueous solution of the chloride of each metal was used.
[279] (4) oxygen permeation rate of EVOH:
[280] Using EVOH pellets, extrusion was carried out at an extrusion temperature of 210 ° C. to obtain a film having a thickness of 20 μm. After heat-treating the film for 10 minutes at a temperature lower than 20 ° C below the melting point of EVOH, the temperature and humidity are adjusted to 20 ° C-65% RH, using an oxygen permeation measuring device (mode control company, OX-TRAN-10 / 50A). Oxygen permeation rate was measured. In the case of using a mixture of two kinds of EVOH as EVOH, two kinds of EVOH pellets were dry blended in advance, a film was obtained according to the above method, and heat treated, and then the oxygen permeation rate was measured. Regarding the EVOH mixture having two melting points, the heat treatment temperature was set to a temperature 20 ° C. lower than the higher melting point.
[281] (5) the number average molecular weight of the copolymer and the number average molecular weight of the styrene block of the copolymer
[282] The number average molecular weight of the copolymer was calculated | required as polystyrene conversion value using gel permeation chromatography (GPC). The number average molecular weight of the styrene block of the copolymer was calculated | required as polystyrene conversion value similarly using GPC using the intermediate sampled after superposition | polymerization of a 1st styrene block as a sample.
[283] (6) the styrene content of the copolymer, the proportion of structural units represented by the formula (I) in the isoprene block and the carbon-carbon double bond content:
[284] All of these were calculated from the spectra obtained by ¹ H-NMR (nuclear magnetic resonance) measurement (using "JNM-GX-500 type" manufactured by Nippon Denshi Corporation) using heavy chloroform as a solvent. Here, styrene content is the ratio (mol%) of styrene with respect to the whole monomeric unit which comprises a copolymer. The ratio of the structural units represented by the general formula (I) in the isoprene block means the general formula (I) with respect to all structural units derived from isoprene (1,4-isoprene unit, 3,4-isoprene unit, and 1,2-isoprene unit). It is the ratio (%) of the structural unit (3, 4- isoprene unit and 1, 2-isoprene unit) shown by these. In addition, from these results, the carbon-carbon double bond content was calculated as the number of moles (eq / g) of the double bonds contained in 1 g of the resin.
[285] (7) tanδ main dispersion peak temperature of the copolymer:
[286] The resin used as a sample was provided to film extrusion at extrusion temperature 210 degreeC, and the unstretched film of 20 micrometers in thickness was obtained. A 5 mm wide test piece was cut out of this film, using DVE RHEOSPECTOLER DVE-V4 (manufactured by RHEOLOGY Co., LTD.), Frequency 11 Hz, displacement amplitude 10 μm, distance between chucks 20 mm, measurement temperature -150 to 150 ° C., heating rate It measured on condition of 3 degree-C / min, and calculated | required tan-delta main dispersion peak temperature derived from the isoprene block of a copolymer from the obtained chart.
[287] (8) melt flow rate:
[288] A chip of a resin or resin composition used as a sample was filled into a cylinder of 9.55 mm in internal diameter and 162 mm in length of the melt indexer L244 (manufactured by Takara Bridge Co., Ltd.), melted at 210 ° C, and then weighed with respect to the melted resin. The load was evenly applied using a plunger having a diameter of 2160 g and a diameter of 9.48 mm. The amount of resin (g / 10 min) extruded per unit time from an orifice having a diameter of 2.1 mm provided at the center of the cylinder was measured, and these were defined as melt flow rates.
[289] (9) refractive index:
[290] The chip | tip of resin used as a sample was provided to film extrusion at extrusion temperature 210 degreeC, and the unstretched film of 20 micrometers in thickness was obtained. The refractive index of this film was measured using Abbe's refractometer (4T type by Atago Co., Ltd., SL-Na-1 lamp by Toshiba Corp.).
[291] (10) Haze value (blur value):
[292] The chip | tip of resin or resin composition used as a sample was provided to film extrusion at extrusion temperature 210 degreeC, and the unstretched film of 20 micrometers in thickness was obtained. The haze value of this film was measured in accordance with ASTM D1003-61 using the pore-integrated sphere light transmittance and a total light reflectometer ("HR-100 type" by Murakami Shiki-Shigizu Tsugyusho Co., Ltd.). In addition, the multilayer film was measured similarly. In addition, regarding a multilayer bottle, the internal haze value in each location was measured about four places which divided the center part of the bottle trunk on the circumference, and made the average value into the haze value (blur value) of a bottle.
[293] (11) Content of each structural unit of PET:
[294] It computed from the spectrum obtained by <^1> H-NMR (nuclear magnetic resonance) measurement (using "JNM-GX1500 type" by Nippon Denshi Corporation) using deuterated trifluoroacetic acid as a solvent.
[295] (12) Ultimate Viscosity of PET:
[296] The film layer of the sample was cut out from the PET layer of the multilayer container trunk | drum, and it melt | dissolved in the equiweight mixed solvent of phenol and tetrachlorethane. The viscosity of the obtained solution was measured at 30 degreeC using the ubelode type viscometer ("HRK-3 type made by Hayashi Seisakusho").
[297] (13) Melting point and glass transition temperature of PET:
[298] The film layer of the sample was cut out from the PET layer of a multilayer container trunk | drum, and it measured using the differential scanning calorimeter (DSC) RDC220 / SSC5200H type by Seiko Dengo Kogyo Co., Ltd. according to JISK7121. After holding the sample at 280 ° C for 5 minutes, the temperature was lowered to 30 ° C at a rate of 100 ° C / min, held for 5 minutes, and then measured at a rate of 10 ° C / min. Indium and lead were used to calibrate the temperature. From the obtained chart, the melting peak temperature (Tpm) and the midpoint glass transition temperature (Tmg) mentioned in the JIS were obtained, and these were taken as the melting point and the glass transition temperature, respectively.
[299] [Resin Used in Examples and Comparative Examples]
[300] In the examples, EVOH was used as the gas barrier resin (A). The physical property of EVOH used by the Example is shown in the following table.
[301] EVOHEthylene contentSaponification degreeMFRPhosphoric Acid ContentSodium salt contentPotassium Salt ContentMagnesium salt contentRefractive indexHazeMelting pointOxygen permeation ratemole%%g / 10 min ^{* 1} ppmppm ^{* 2} ppm ^{* 2} ppm ^{* 2} %℃ml, 20μm / ㎡, day, atm A-11A-12A-1344323299.599.599.513.310.08.49510010085100205090604545201.5281.5331.5331.00.80.71651831831.50.40.4 A-214496.512.2857033251.5280.51523.0
[302] * 1: 210 ° C, 2160g
[303] * 2: all metal equivalent
[304] As the thermoplastic resin (B), a triblock copolymer (B-1) prepared by the following method was used.
[305] 600 volume parts of cyclohexane, 0.16 volume parts of N, N, N ', N'-tetramethylethylenediamine (TMEDA), and 0.094 volume parts of n-butyllithium as an initiator were charged to the stirred autoclave purified with dry nitrogen. The temperature was raised to 50 ° C., 4.25 parts by volume of styrene monomer was supplied and polymerized for 1.5 hours. Then, the temperature was lowered to 30 ° C, 120 parts by volume of isoprene was supplied and polymerized for 2.5 hours. Furthermore, temperature was heated up at 50 degreeC again, 4.25 volume parts of styrene monomers were supplied, and it superposed | polymerized for 1.5 hours.
[306] To the obtained reaction solution, 2-3-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and pentaerythritol tetrakis (3-la) as antioxidants Urylthiopropionate) was added in an amount of 0.15 parts by weight based on 100 parts by weight of the total amount of styrene and isoprene, respectively. The reaction solution was poured into methanol to precipitate the product, which was separated and dried to obtain a triblock copolymer (B-1) to which an antioxidant was added.
[307] The number average molecular weight of the obtained styrene-isoprene-styrene triblock copolymer (B-1) is 85000, the molecular weight of the styrene block in the copolymer is 8500, the styrene content is 14 mol%, and is represented by the general formula (I) in the isoprene block. The proportion of structural units was 55%. The carbon-carbon double bond content of the copolymer was 0.014 eq / g, and the melt flow rate (210 ° C., 2160 g load) was 7.7 g / 10 min. In the copolymer (B-1), 0.12% by weight of 2-3-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and pentaerythritol tetrakis 0.12-% by weight of (3-laurylthiopropionate) was included. The refractive index of this copolymer (B-1) was 1.531, the haze value (blur value) was 1.0%, and the tanδ main dispersion peak temperature derived from the isoprene block was -3 ° C. As the compatibilizer (C), the polymer shown in the following table was used.
[308] CompatibilizerpolymerType of functional group contained C-1Styrene-hydrogenated butadiene-styrene triblock copolymers with boron-containing polar groupsBoronic acid 1,3-butanediol ester group C-2Styrene-hydrogenated butadiene-styrene triblock copolymers with boron-containing polar groupsBoronic acid 1,3-butanediol ester group C-3Ethylene-Methacrylic Acid CopolymerCarboxyl group
[309] The compatibilizer (C-1) was prepared as follows.
[310] 500 parts by weight of a styrene-hydrogenated butadiene-styrene tree block copolymer ("Tafutec (trademark) H1062" manufactured by Asahi Kasei Co., Ltd.) to a reactor equipped with a stirrer, a nitrogen introduction pipe, a cooler, and a distillation machine, and 1,500 parts by weight of decalin was added and the reaction tank was replaced with nitrogen, and then the temperature was set to 130 ° C and stirred to dissolve the copolymer. Furthermore, 57.5 weight part of borane triethylamine complexes and 143 weight part of boric acid 1, 3- butanediol esters were added to the reaction tank. After stirring for 5 minutes, stirring was stopped once and the temperature of the reaction tank was heated up to 200 degreeC. After raising the temperature, if left for a while, the entire solution gelled, and then the dissolution of the gel gradually progressed on the wall surface. Stirring was started again when the stirring became possible, and stirring was continued for 1 hour after the gel in a reaction tank disappeared completely. The cooler was changed to a still, the temperature of the reaction tank was raised to 220 ° C., distillation was started at normal pressure, and distillation was continued until the effluent disappeared. The obtained reaction liquid was cooled, poured into acetone, the product was precipitated, separated, and vacuum dried at 120 ° C. overnight to obtain a triblock copolymer (C-1). The copolymer was dissolved in a mixed solvent in the ratio of medium paraxylene: heavy chloroform: ethylene glycol = 8: 2: 0.02 and provided for ¹ H-NMR measurement (500 MHz). The butanediol ester group content was 220 µeq / g.
[311] Compatibilizer (C-2) was prepared as follows.
[312] Styrene-hydrogenated butadiene-styrene triblock copolymer [weight average molecular weight 100400, styrene / hydrogenated butadiene = 18/82 (weight ratio), 1,2-bond / 1,4-bond molar ratio of butadiene units = 47/53 , Hydrogenation rate of butadiene unit 97%, double bond amount 430μeq / g, melt index 5g / 10min (230 ° C, 2160g load), density 0.89g / cm3], while replacing the inlet with 1L / min nitrogen, 7kg / It was fed to a twin screw extruder at the speed of time. Next, in the liquid feeder 1, the mixed liquid (TEAB / BBD = 29/71, weight ratio) of the boranetriethylamine complex (TEAB) and boric acid 1,3-butanediol ester (BBD) was fed at a rate of 0.6 kg / hr. 2,1,3-butanediol was fed at a rate of 0.4 kg / hr and kneaded continuously. During the kneading, the pressure was adjusted such that the gauges of Vent 1 and Vent 2 showed about 20 mm Hg. As a result, a triblock copolymer (C-2) containing boronic acid 1,3-butanediol ester group (BBDE) was obtained at a rate of 7 kg / hr from the discharge port. The boronic acid 1,3-butanediol ester group amount of this copolymer was 210 microeq / g.
[313] In addition, the structure and operation conditions of the twin screw extruder used for reaction are as follows.
[314] Coaxial twin screw extruder TEM-35B
[315] Screw diameter: 37 mmø
[316] L / D: 52 (15 blocks)
[317] Liquid feeder: C3 (liquid feeder 1), C11 (liquid feeder 2)
[318] Vent position: C6 (Bent 1), C14 (Bent 2)
[319] Screw configuration: Use sealing rings in positions C5-C6, C10-C11 and C12
[320] Temperature setting: C1 water cooling
[321] C2 to C3200 ℃
[322] C4 to C1525O ℃
[323] Die 250 ℃
[324] Screw speed: 400rpm
[325] In addition, as a compatibilizer (C-3), the ethylene-methacrylic acid copolymer ("Neucrerel (brand name)" N-1207C by Mitsui Dupont Polychemical Co., Ltd.) was used.
[326] As the thermoplastic polyester, polyethylene terephthalate (PET) obtained by polymerization using germanium dioxide as a catalyst was used. The content rates of terephthalic acid unit, ethylene glycol unit, and diethylene glycol unit in the PET were 50.0 mol%, 48.9 mol%, and 1.1 mol%, respectively. Moreover, intrinsic viscosity was 0.83 dl / g, melting | fusing point, and glass transition temperature was 252 degreeC and 80 degreeC, respectively.
[327] Example 1
[328] 71.4 parts by weight of the triblock copolymer (B-1), 28.6 parts by weight of the compatibilizer (C-1) and 3.0300 parts by weight of cobalt (II) stearate (0.2857 parts by weight as a cobalt atom) were dry blended to form a 30 mm ø twin screw extruder ( TEX-30SS-30CRW-2V manufactured by Nippon Seiko Sho Co., Ltd.) was extruded and pelletized at 200 ° C. under nitrogen purging under a condition of a screw rotation speed of 300 rpm and an extrusion resin amount of 25 kg / hour. It dried under reduced pressure at 30 degreeC for 8 hours, and obtained the resin composition pellet which consists of a triblock copolymer (B-1), a compatibilizer (C-1), and cobalt stearate. Using the obtained resin composition pellets, extrusion molding was performed at extrusion temperature 210 degreeC, and the film (1st single layer film) of 20 micrometers in thickness was obtained. The haze value of this film was 1.8%. 0.9 m 2 (0.2 m x 4.5 m; surface area 1.8 m 2) of the film was rolled up into a roll after 5 hours of film production, and placed in a Erlenmeyer flask with an internal capacity of 375 ml filled with air at 20 ° C. and 65% RH. The air in the Erlenmeyer flask contained 21:79 oxygen and nitrogen in volume ratio. The inlet of the Erlenmeyer flask was sealed with a multilayer sheet containing an aluminum layer using an epoxy resin, and then left at 20 ° C. After 2 days of encapsulation, the air inside after 4 days and after 8 days was sampled with a syringe, and the oxygen concentration of this air was measured using gas chromatography. The pores perforated in the multilayer sheet at the time of measurement were sealed each time using an epoxy resin. The amount of oxygen reduction (oxygen uptake) was calculated from the volume ratio of oxygen and nitrogen obtained by the measurement, and the results shown in FIG. 1 were obtained. The oxygen absorption rate of the film calculated from the measurement results after 2 days and after 8 days was 67 ml / m 2 · day.
[329] 93 parts by weight of EVOH (A-11) shown in Table 2 and 7.2121 parts by weight of the above resin composition were dry blended at 210 ° C. using a 30 mm ø twin screw extruder (TEX-30SS-30CRW-2V manufactured by Nippon Seiko Sho Co., Ltd.). It extruded and pelletized on the conditions of a screw speed of 300 rpm and 25 kg / hour of extrusion resins, and it dried under reduced pressure at 30 degreeC for 16 hours, and obtained the resin composition pellets. The melt flow rate (210 ° C., 2160 g load) of this resin composition was 13.1 g / 10 min. When the fracture surface of the resin composition pellets was observed under an electron microscope, particles of approximately 1 μm or less of the triblock copolymer (B-1) were found. Was dispersed in a matrix composed of EVOH.
[330] It was 1.3% when the film (2nd single layer film) of 20 micrometers in thickness was obtained from this resin composition in the same manner to the above, and haze value was measured. Moreover, when the oxygen absorption amount was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the film was 1.238 ml / m 2 · day.
[331] Next, a stretched polypropylene film (OP- # 20 U-1 manufactured by Tosei Industries Co., Ltd.) having a thickness of 20 μm was placed on both surfaces of the obtained film, and a urethane-based adhesive (made by Toyota Moton, trade name: AD335A) and a curing agent (made by Toyota Moton) And a toluene / methyl ethyl ketone mixed solution (weight ratio 1: 1) of the product name: Cat-10) were laminated, and the multilayer film was obtained. The haze value of this multilayer film was 2.7%. Oxygen permeation rate was controlled using an oxygen permeation measuring apparatus (OX-TRAN-10 / 50A, manufactured by Modern Control, Inc.), with the temperature and humidity controlled at 20 ° C.-85% RH and 24 hours after film formation being O. Was measured for 1000 hours, and the result shown in FIG. 3 was obtained.
[332] Next, using the resin composition pellets and the above-mentioned PET as raw materials, using a constant ASB construction-stretched blow molding machine (500 ml of ASB-50HT type), Parisson of two kinds and three layers of PET / resin composition / PET Was molded. At this time, the PET side injection machine temperature is 290 ° C, the resin composition side injection machine temperature is 205 ° C, the temperature of the hot runner block portion where PET and the resin composition join is 255 ° C, the injection mold core temperature is 15 ° C, and the injection mold cavity temperature is 15 ℃. In addition, the cycle time was 40 seconds. Thereafter, using a stretch blow molding machine (LB01) manufactured by CORPOPLAST Co., Ltd., the surface temperature of the flyson was heated to 105 ° C. to carry out the stretch blow molding, and the average thickness at the trunk portion was 100 μm of the inner layer PET and the intermediate layer. The resin composition was 15 micrometers and outer layer PET 150 micrometers, and the bottom part produced the 2 types and 3 layer multilayer injection blow molding bottle of the champagne bottle shape. The haze value of this disease was 3.0%.
[333] The obtained bottle was temperature-humidity adjusted to 20 degreeC-65% RH outside a bottle and 20 degreeC-100% RH inside a bottle, and it shape | molded using the oxygen permeation measuring apparatus (made by Modern Control, OX-TRAN-10 / 50A) for 10 days. It was 0.00 ml / container day atm when the oxygen permeation rate per one container was measured.
[334] In contrast to this, the bottle was filled with water as the contents, and the bottle was sealed under normal pressure. From the height of 50 cm in the state where the bottle body was made vertical, the bottle bottom was naturally dropped on the horizontal concrete plate only once. It was 7% when 100 tests were performed about one type of bottle, and the delamination generation rate Rd (%) was computed by the following formula from the number Nd of bottles which produced the delamination.
[335] Rd = (Nd / 100) × 100
[336] Example 2
[337] 71.4 parts by weight of the triblock copolymer (B-1) and 28.6 parts by weight of the compatibilizer (C-1) used in Example 1 were dry blended, and 30 mm ø twin screw extruder (TEX-30 SS-30CRW-2V manufactured by Nippon Seigo Sho Co., Ltd.) ) Was extruded and pelletized at 200 ° C under conditions of a screw speed of 300 rpm and an amount of extruded resin of 25 kg / hour, while purging the cylinder with nitrogen. It dried under reduced pressure at 30 degreeC for 8 hours, and obtained the resin composition pellet which consists of a triblock copolymer (B-1) and a compatibilizer (C-1).
[338] It was 1.6% when the film of 20 micrometers in thickness was obtained from this resin composition similarly to Example 1, and haze value was measured.
[339] 74.4 parts by weight of EVOH (A-11) used in Example 1, 18.6 parts by weight of EVOH (A-21) shown in Table 2, and the above-described triblock copolymer (B-1) and a compatibilizer (C-1). A resin composition was obtained in the same manner as in Example 1 using 7 parts by weight of the resin composition and 0.2121 parts by weight of cobalt (II) stearate (0.0200 parts by weight as a cobalt atom). The melt flow rate (210 degreeC, 2160g load) of this resin composition was 12.8g / 10min. When the fracture surface of the resin composition pellets was observed with an electron microscope, particles of approximately 1 μm or less of the triblock copolymer (B-1) were dispersed in a matrix composed of EVOH.
[340] It was 1.2% when the film of 20 micrometers in thickness was obtained from this resin composition similarly to Example 1, and haze value was measured. Moreover, when the oxygen absorption amount was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the film was 1.475 ml / m 2 · day. Next, it was 2.5% when the multilayer film was produced like Example 1, and haze value was measured. Moreover, when the oxygen permeation rate was measured over time, the result shown in FIG. 3 was obtained.
[341] Moreover, it was 2.8% when the bottle was produced like Example 1, and haze value was measured. The oxygen permeation rate of this bottle was measured in the same manner as in Example 1 and found to be 0.00 ml / container day atm. When the drop test was conducted in the same manner as in Example 1, the rate of delamination was 1%.
[342] Example 3
[343] In Example 2, the resin composition was obtained like Example 2 except having used EVOH (A-12) shown in Table 2 instead of EVOH (A-11). The melt flow rate (210 degreeC, 2160g load) of this resin composition was 9.2g / 10min. When the fracture surface of the resin composition pellets was observed with an electron microscope, particles of approximately 1 μm or less of the triblock copolymer (B-1) were dispersed in a matrix composed of EVOH.
[344] It was 1.4% when the film of 20 micrometers in thickness was obtained from this resin composition similarly to Example 1, and haze value was measured. Moreover, when the oxygen absorption amount was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the film was 0.938 ml / m 2 · day. Next, it was 2.7% when the multilayer film was produced like Example 1, and haze value was measured. Moreover, when the oxygen permeation rate was measured over time, the result shown in FIG. 3 was obtained.
[345] Moreover, it was 2.9% when the bottle was produced like Example 1, and haze value was measured. The oxygen permeation rate of this bottle was measured in the same manner as in Example 1 and found to be 0.00 ml / container day atm. When the drop test was conducted in the same manner as in Example 1, the rate of delamination was 3%.
[346] Example 4
[347] In Example 3, the resin composition was obtained like Example 3 except having used the compatibilizer (C-2) instead of the compatibilizer (C-1). The melt flow rate (210 degreeC, 2160g load) of this resin composition was 9.2g / 10min. When the fracture surface of the resin composition pellets was observed with an electron microscope, particles of approximately 1 μm or less of the triblock copolymer (B-1) were dispersed in a matrix composed of EVOH.
[348] It was 1.4% when the film of 20 micrometers in thickness was obtained from this resin composition similarly to Example 1, and haze value was measured. Moreover, when the oxygen absorption amount was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the film was 1.044 ml / m 2 · day. Next, it was 2.8% when the multilayer film was produced like Example 1, and haze value was measured. Moreover, when the oxygen permeation rate was measured over time, the result shown in FIG. 3 was obtained.
[349] Moreover, it was 3.0% when the bottle was produced like Example 1 and the haze value was measured. The oxygen permeation rate of this bottle was measured in the same manner as in Example 1 and found to be 0.00 ml / container day atm. When the drop test was conducted in the same manner as in Example 1, the rate of delamination was 2%.
[350] Example 5
[351] 94 parts by weight of EVOH (A-13) shown in Table 2, 5 parts by weight of the triblock copolymer (B-1), 1 part by weight of a compatibilizer (C-3), and 0.2121 parts by weight of cobalt (II) stearate (cobalt atom Was used in the same manner as in Example 1 to obtain a resin composition. The melt flow rate (210 degreeC, 2160g load) of this resin composition was 9.4g / 10min. When the fracture surface of the resin composition pellet was observed with the electron microscope, the particle | grains of about 1 micrometer of the triblock copolymer (B-1) were disperse | distributing in the matrix which consists of EVOH.
[352] In order to evaluate the thermal stability of this resin composition, a differential thermal thermogravimetry simultaneous measurement device (TG / DTA220 type and SSC5200H type manufactured by Seiko Denso Kogyo Co., Ltd.) was used, and the resin composition pellets were kept at 10 ° C / under a nitrogen atmosphere. It heated up from room temperature to 260 degreeC at the rate of minutes, and hold | maintained at 260 degreeC for 2 hours, The weight retention rate of the pellet (weight ratio of the pellets based on the weight before heating) was 98.5%.
[353] It was 1.1% when the film of 20 micrometers in thickness was obtained from this resin composition pellet similarly to Example 1, and haze value was measured. In addition, the oxygen absorption amount was measured similarly to Example 1 except having set the sampling time to 2 days after sealing, 6 days after, and 13 days after, and the result shown in FIG. 4 was obtained. It was computed from the measurement result after 2 days and after 13 days, and the oxygen absorption rate of the film was 0.525 ml / m <2> * day. Next, it was 2.4% when the multilayer film was produced like Example 1, and haze value was measured. Moreover, when the oxygen permeation rate was measured over time, the result shown in FIG. 5 was obtained.
[354] Next, using the resin composition pellets and the above-mentioned PET as raw materials, a Nissei ASB-made stretched blow molding machine (750 ml of ASB-50HT type, two) was used, and PET / resin composition / PET Two and three layers of Parison were molded.
[355] At this time, the PET side injection machine temperature is 290 ° C, the resin composition side injection machine temperature is 220 ° C, the temperature of the hot runner block portion where the PET and the resin composition join is 260 ° C, the injection mold core temperature is 15 ° C, and the injection mold cavity temperature is 15 ℃. The cycle time was 40 seconds. Thereafter, using a stretch blow molding machine (LB01) manufactured by CORPOPLAST, the surface temperature of the parison was heated to 105 ° C. to carry out the stretch blow molding, A multilayer injection blow molding bottle of two kinds and three layers, in which the average thickness of the inner layer PET was 200 mu m, the middle layer resin composition 20 mu m, and the outer layer PET 70 mu m, was prepared. The haze of this disease was 2.9%.
[356] The obtained bottle was adjusted to temperature and humidity at 20 ° C.-65% RH outside the bottle and 20 ° C.-100% RH inside the bottle, and the 10th molding was performed by using an oxygen permeation measuring device (OX-TRAN-10 / 50A, manufactured by Modern Control). It was 0.00 ml / container day atm when the oxygen permeation rate per one container was measured. The outside of the bottle was kept at 20 ° C.-65% RH under nitrogen atmosphere and the inside of the bottle at 20 ° C.-100% RH under nitrogen atmosphere, and the bottle was stored for 3 months, and the oxygen permeation rate per container was measured. ml / container day atm.
[357] Moreover, when the said bottle was shape | molded continuously and the external appearance of the bottle after 12 hours of continuous operation was observed visually, the external appearance defects, such as air bubble, were not seen at all.
[358] Example 6
[359] 100 parts by weight of a compatibilizer (C-3) and 3 parts by weight of cobalt (II) acetate (1 part by weight as a cobalt atom) are dry blended, and a lavoplasm mill (manufactured by Toyo Seiki Co., Ltd.) Was melt kneaded at a rotational speed of 60 rpm for 5 minutes at 220 ° C. under a nitrogen atmosphere. The neutralization reaction started immediately after the input of the raw material, and the generation of acetic acid vapor, which was a by-product, was confirmed, but at the end of the kneading, the steam was collected. Thus, 101 parts by weight of a dark blue compatibilizer composition was obtained.
[360] The resin composition was obtained like Example 1 using 93 weight part of EVOH (A-13) used in Example 5, 5 weight part of triblock copolymers (B-1), and 2.02 weight part of said compatibilizer compositions. . The melt flow rate (210 degreeC, 2160g load) of this resin composition was 9.6g / 10min. When the fracture surface of the resin composition pellets was observed with an electron microscope, particles around 1 μm of the triblock copolymer (B-1) were dispersed in a matrix composed of EVOH. The thermal stability of this resin composition was evaluated in the same manner as in Example 5, and the weight retention of the pellet was 99.4%.
[361] It was 1.6% when the film of 20 micrometers in thickness was obtained from this resin composition similarly to Example 5, and haze value was measured. Moreover, when the oxygen absorption amount was measured, the result shown in FIG. 4 was obtained. The oxygen absorption rate of the film was 0.507 ml / m 2 · day. Next, it was 2.7% when the multilayer film was produced like Example 5, and haze value was measured.
[362] Moreover, it was 3.4% when the bottle was produced like Example 5 and the haze value was measured. The oxygen permeation rate of this bottle was measured in the same manner as in Example 5 and found to be 0.00 ml / container day atm. The oxygen permeation rate of the bottle after 3 months of storage was 0.00 ml / container day atm.
[363] Moreover, when the said bottle was shape | molded continuously and the external appearance of the bottle after 12 hours of continuous operation was observed visually, the external appearance defects, such as air bubble, were not seen at all.
[364] Example 7
[365] 101 weight part of a dark blue compatibilizer composition was carried out similarly to Example 6 except having used 10.6 weight part cobalt (II) stearic acid (1 weight part as a cobalt atom) instead of 3 weight part of cobalt acetate (II). Got wealth.
[366] The resin composition was obtained like Example 6 except having changed the compatibilizer composition into said composition. The melt flow rate (210 degreeC, 2160g load) of this resin composition was 9.6g / 10min. When the fracture surface of the resin composition pellets was observed with an electron microscope, particles around 1 μm of the triblock copolymer (B-1) were dispersed in a matrix composed of EVOH. In addition, when the thermal stability of this resin composition was evaluated like Example 5, the weight retention of the pellet was 99.3%.
[367] It was 1.4% when the film of 20 micrometers in thickness was obtained from this resin composition similarly to Example 5, and haze value was measured. Moreover, when the oxygen absorption amount was measured, the result shown in FIG. 4 was obtained. The oxygen absorption rate of the film was 0.471 ml / m 2 · day. Next, it was 2.8% when the multilayer film was produced like Example 5, and haze value was measured.
[368] Moreover, it was 3.2% when the bottle was produced like Example 5 and the haze value was measured. The oxygen permeation rate of this bottle was measured in the same manner as in Example 5 and found to be 0.00 ml / container day atm. The oxygen permeation rate of the bottle after 3 months of storage was 0.00 ml / container day atm.
[369] Moreover, when the said bottle was shape | molded continuously and the external appearance of the bottle after 12 hours of continuous operation was observed visually, the external appearance defects, such as air bubble, were not seen at all.
[370] Comparative Example 1
[371] EVOH (A-11) was used alone and in the same manner as in Example 1, a film having a thickness of 20 μm was obtained. When the oxygen absorption amount of this film was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the film was 0.000 ml / m 2 · day. Next, it was 2.1% when the multilayer film was produced like Example 1, and haze value was measured. Moreover, when the oxygen permeation rate was measured over time, the result shown in FIG. 3 was obtained.
[372] Moreover, it was 2.1% when the bottle was produced like Example 1 and the haze value was measured. The oxygen permeation rate of this bottle was measured in the same manner as in Example 1 and found to be 0.03 ml / container day atm. When the drop test was conducted in the same manner as in Example 1, the rate of delamination was 10%.
[373] Comparative Example 2
[374] 95 parts by weight of EVOH (A-11) used in Example 1, 5 parts by weight of a triblock copolymer (B-1), and 0.2121 parts by weight of cobalt (II) stearate (0.0200 parts by weight as a cobalt atom) were used. In the same manner as in Example 1, a resin composition was obtained. The melt flow rate (210 degreeC, 2160g load) of this resin composition was 13.5g / 10min. When the fracture surface of the resin composition pellets was observed with an electron microscope, particles of approximately 1 to 2 탆 of the triblock copolymer (B-1) were dispersed in a matrix composed of EVOH.
[375] It was 1.5% when the film of 20 micrometers in thickness was obtained from this resin composition similarly to Example 1, and haze value was measured. Moreover, when the oxygen absorption amount was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the film was 1.117 ml / m 2 · day. Next, it was 2.9% when the multilayer film was produced like Example 1, and haze value was measured. Moreover, when the oxygen permeation rate was measured over time, the result shown in FIG. 3 was obtained.
[376] Moreover, it was 3.3% when the bottle was produced like Example 1 and the haze value was measured. The oxygen permeation rate of this bottle was measured in the same manner as in Example 1 and found to be 0.00 ml / container day atm. When the drop test was conducted in the same manner as in Example 1, the rate of delamination was 52%.
[377] Comparative Example 3
[378] A film having a thickness of 20 μm was obtained in the same manner as in Comparative Example 1 except that EVOH (A-12) was used alone instead of EVOH (A-11). When the oxygen absorption amount of this film was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the film was 0.000 ml / m 2 · day. Next, it was 2.0% when the multilayer film was produced like Example 1, and haze value was measured. Moreover, when the oxygen permeation rate was measured over time, the result shown in FIG. 3 was obtained.
[379] Moreover, it was 2.0% when the bottle was produced like Example 1 and the haze value was measured. The oxygen permeation rate of this bottle was measured in the same manner as in Example 1 and found to be 0.02 ml / container day atm. When the drop test was conducted in the same manner as in Example 1, the rate of delamination was 11%.
[380] Comparative Example 4
[381] A resin composition was obtained in the same manner as in Comparative Example 2 except that EVOH (A-12) was used instead of EVOH (A-11). The melt flow rate (210 degreeC, 2160g load) of this resin composition was 10.0g / 10min. When the fracture surface of the resin composition pellets was observed with an electron microscope, approximately 1 to 2 탆 of particles of the triblock copolymer (B-1) were dispersed in a matrix composed of EVOH.
[382] It was 1.4% when the film of 20 micrometers in thickness was obtained from this resin composition similarly to Example 1, and haze value was measured. Moreover, when the oxygen absorption amount was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the film was 0.700 ml / m 2 · day. Next, it was 2.9% when the multilayer film was produced like Example 1, and haze value was measured. Moreover, when the oxygen permeation rate was measured over time, the result shown in FIG. 3 was obtained.
[383] Moreover, it was 3.4% when the bottle was produced like Example 1 and the haze value was measured. The oxygen permeation rate of this bottle was measured in the same manner as in Example 1 and found to be 0.00 ml / container day atm. When the drop test was carried out in the same manner as in Example 1, the rate of lamination was 85%.
[384] Comparative Example 5
[385] EVOH (A-13) was used alone. When the thermal stability of this EVOH was evaluated in the same manner as in Example 5, the weight retention of the pellets of the EVOH was 91.4%. A film having a thickness of 20 µm was obtained in the same manner as in Example 5, and the oxygen absorption amount was measured. The results shown in FIG. 4 were obtained. The oxygen absorption rate of the film was 0.000 ml / m 2 · day. Next, it was 2.0% when the multilayer film was produced like Example 5, and haze value was measured. Moreover, when the oxygen permeation rate was measured over time, the result shown in FIG. 5 was obtained.
[386] Moreover, it was 2.4% when the bottle was produced like Example 5 and the haze value was measured. The oxygen permeation rate of this bottle was measured in the same manner as in Example 5 and found to be 0.02 ml / container day atm. The oxygen permeation rate of the bottle after storage for 3 months was 0.02 ml / container day atm.
[387] Moreover, when the said bottle was shape | molded continuously and the external appearance of the bottle after 12 hours of continuous operation was observed visually, the external appearance defects, such as a bubble, were not seen at all.
[388] Comparative Example 6
[389] 95 parts by weight of EVOH (A-13) used in Example 5, 5 parts by weight of the triblock copolymer (B-1) and 0.2121 parts by weight of cobalt (II) stearate (0.0200 parts by weight as a cobalt atom) were used In the same manner as in Example 5, a resin composition was obtained. The melt flow rate (210 degreeC, 2160g load) of this resin composition was 9.5g / 10min. When the fracture surface of the resin composition pellets was observed with an electron microscope, particles around 1 μm of the triblock copolymer (B-1) were dispersed in a matrix composed of EVOH. In addition, when the thermal stability of this resin composition was evaluated like Example 5, the weight retention of the pellet was 83.0.
[390] It was 1.0% when the film of 20 micrometers in thickness was obtained from this resin composition similarly to Example 1, and haze value was measured. Moreover, when the oxygen absorption amount was measured, the result shown in FIG. 4 was obtained. The oxygen absorption rate of the film was 0.565 ml / m 2 · day. Next, it was 2.3% when the multilayer film was produced like Example 1, and haze value was measured. Moreover, when the oxygen permeation rate was measured over time, the result shown in FIG. 5 was obtained.
[391] Moreover, it was 2.7% when the bottle was produced like Example 5 and the haze value was measured. The oxygen permeation rate of this bottle was measured in the same manner as in Example 5 and found to be 0.00 ml / container day atm. The oxygen permeation rate of the bottle after 3 months of storage was 0.00 ml / container day atm.
[392] Moreover, when the said bottle was shape | molded continuously and the external appearance of the bottle after 12 hours of continuous operation was observed visually, some bubble was confirmed.
[393] The structure of said resin composition is put together in Table 4, and the result of various evaluations is put together in Table 5 and Table 6, and is shown.
[394] Resin compositionEVOH (A)Thermoplastic resinCompatibilizer (C)Transition metal saltEVOH (a1)Parts by weightEVOH (a2)Parts by weightMelting Point (℃)Oxygen Transmission Rate ^{* 9} Parts by weightCompatibilizerParts by weightppm ^{* 3}Example 1A-1193.0--1651.55.0C-12.0200 Example 2A-1174.4A-2118.61621.75.0C-12.0200 Example 3A-1274.4A-2118.6182,1530.65.0C-12.0200 Example 4A-1274.4A-2118.6182,1530.65.0C-22.0200 Example 5A-1394.0--1830.45.0C-31.0200 Example 6A-1393.0--1830.45.0C-32.0200 Example 7A-1393.0--1830.41.55.0C-32.0200 Comparative Example 1A-11100.0--1651.5---- Comparative Example 2A-1195.0--1651.55.0--200 Comparative Example 3A-12100.0--1830.4---- Comparative Example 4A-1295.0--1830.45.0--200 Comparative Example 5A-13100.0--1830.4---- Comparative Example 6A-1395.0--1830.45.0--200
[395] * 3: metal equivalent
[396] * 9: ml, 20 μm / m 2, day, atm
[397] Resin compositionMultilayer filmbottle MFRHazeOxygen Absorption Rate ^{* 5} HazeHazeOxygen transmission rateDelamination occurrence rate g / 10 min ^{* 4} %ml / ㎡day%%ml / containerdayatm% Example 113.11.31.2382.73.00.007 Example 212.81.21.4752.52.80.00One Example 39.21.40.9382.72.90.003 Example 49.21.41.0442.83.00.002 Comparative Example 113.31.00.0002.12.10.0310 Comparative Example 213.51.51.1172.93.30.0052 Comparative Example 310.00.80.0002.02.00.0211 Comparative Example 410.01.40.7002.93.40.0085
[398] * 4: 210 ° C, 2160g
[399] * 5: Calculated from oxygen absorption after 2 days and 8 days
[400] Resin compositionMultilayer filmbottle MFRHazeOxygen Absorption Rate ^{* 6} Weight retentionHazeHazeOxygen Transmission Rate ^{* 7} Oxygen Transmission Rate ^{* 8} Exterior g / 10 min ^{* 4} %ml / ㎡day%%%ml / containerdayatmml / containerdayatmExample 59.41.10.52598.52.42.90.000.00Good Example 69.61.60.50799.42.73.40.000.00Good Example 79.61.40.47199.32.83.20.000.00Good Comparative Example 58.40.70.00091.42.02.40.020.02Good Comparative Example 69.51.00.56583.02.32.70.000.00Somewhat poor
[401] * 4: 210 ° C, 2160g
[402] * 6: Calculated from oxygen uptake after 2 days and after 13 days
[403] * 7: Oxygen permeation rate of bottle 10 days after molding
[404] * 8: Oxygen permeation rate of bottle 3 months after molding
[405] Example 8
[406] The multilayer film produced in Example 5 was punched into the shape of a gasket so that it might fit in the polypropylene screw cap main body of 65 mm of outer diameter and 1.2 mm of bottom part thickness, and was attached to this screw cap main body. Subsequently, a cap with a gasket obtained was supplied to a mold of a gasket molding machine for compression molding, and an ethylene-1-butene copolymer [“POLYBUTYLENE 8240 made by Shell Chemicals”: 1-butene (99 mol% or more) was supplied to the compression molding gasket molding machine. ) And a copolymer of ethylene (1 mol% or less), density 0.908 g / cm 3 and MFR = 2.0 g / 10 min (210 ° C., 2160 g load)] are supplied to the gasket surface made of the multilayer film, followed by compression molding. The cap with a multilayer gasket was produced. At this time, the cylinder temperature of the compression molding machine was adjusted to 245 ° C, the nozzle temperature to 235 ° C, and the mold temperature to 30 ° C.
[407] Next, 200 ml of water was put into the cylindrical polyester blow bottle of 500 ml of contents, and the said cap was attached, and it was lightly tightened by the fingertip. While holding the bottle body in hand and shaking it up and down 20 times, the state of liquid leakage was observed, but liquid leakage was not seen at all.
[408] According to this invention, the resin composition which has the outstanding oxygen scavenging function is obtained. The said resin composition is easy to handle and can be shape | molded in arbitrary shapes. In particular, the container made of the resin composition not only has excellent gas barrier property, moisture resistance, steering ability, and flaver barrier property, but also has excellent impact peel resistance and can obtain an appearance and particularly high transparency. It is useful as a container for products such as foods, beverages, medicines, and cosmetics, which are highly susceptible to oxygen and susceptible to deterioration.

权利要求:
Claims (25)
[1" claim-type="Currently amended] A resin composition containing a gas barrier resin (A), a thermoplastic resin (B) other than the gas barrier resin (A), and a compatibilizer (C), wherein an oxygen permeation rate of the gas barrier resin (A) is 500 ml. 20 µm / m 2 day atm (20 ° C., 65% RH) or less, the thermoplastic resin (B) has a carbon-carbon double bond, and the oxygen absorption rate of the resin composition is 0.001 ml / m 2 · day or more. Resin composition.
[2" claim-type="Currently amended] The resin composition of Claim 1 which further contains a transition metal salt (D).
[3" claim-type="Currently amended] A resin composition containing a gas barrier resin (A), a thermoplastic resin (B) other than the gas barrier resin (A), a compatibilizer (C), and a transition metal salt (D), wherein the gas barrier resin (A) The resin composition having an oxygen permeation rate of 500 ml · 20 μm / m 2 · at · m (20 ° C., 65% RH) or less, wherein the thermoplastic resin (B) has a carbon-carbon double bond.
[4" claim-type="Currently amended] The transition metal salt (D) is 1 to 5000 ppm in terms of metal elements according to claim 2 or 3, based on the total weight of the gas barrier resin (A), the thermoplastic resin (B), and the compatibilizer (C). Resin composition contained in the ratio of.
[5" claim-type="Currently amended] The resin composition according to any one of claims 2 to 4, wherein the transition metal salt (D) has at least one transition metal selected from the group consisting of iron, nickel, copper, manganese and cobalt.
[6" claim-type="Currently amended] The resin composition according to any one of claims 1 to 5, wherein the thermoplastic resin (B) contains a carbon-carbon double bond at a ratio of 0.0001 eq / g or more.
[7" claim-type="Currently amended] The resin composition according to any one of claims 1 to 6, wherein the thermoplastic resin (B) has a unit represented by the following general formula (I).
Formula I

In Formula I,
R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R ₂ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group,
R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group which may be substituted, -COOR ₅ , -OCOR ₆ , a cyano group or a halogen atom,
R ₅ and R ₆ are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group.
[8" claim-type="Currently amended] The resin composition of any one of Claims 1-7 whose number average molecular weights of a thermoplastic resin (B) are 1000-50000.
[9" claim-type="Currently amended] The resin composition according to any one of claims 1 to 8, wherein the gas barrier resin (A) is an ethylene-vinyl alcohol copolymer having an ethylene content of 5 to 60 mol% and a saponification degree of 90% or more.
[10" claim-type="Currently amended] The resin composition according to any one of claims 1 to 9, wherein a difference in refractive index between the gas barrier resin (A) and the thermoplastic resin (B) is 0.01 or less.
[11" claim-type="Currently amended] The resin composition according to any one of claims 1 to 10, wherein particles made of a thermoplastic resin (B) are dispersed in a matrix of the gas barrier resin (A).
[12" claim-type="Currently amended] The gas barrier resin (A) at a ratio of 40 to 99.8 wt%, the thermoplastic resin (B) at a ratio of 0.1 to 30 wt%, and a compatibilizer ( A resin composition containing C) in a proportion of 0.1 to 30% by weight.
[13" claim-type="Currently amended] A resin composition containing a thermoplastic resin (B) and a compatibilizer (C), wherein the thermoplastic resin (B) has a unit represented by the following general formula (I) and further contains a carbon-carbon double bond at a rate of 0.0001 eq / g or more And the number average molecular weight of the said thermoplastic resin (B) is 1000-50000, and the resin composition whose oxygen absorption rate of a resin composition is 0.1 ml / m <2> * day or more.
Formula I

In Formula I,
R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R ₂ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group,
R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group which may be substituted, -COOR ₅ , -OCOR ₆ , a cyano group or a halogen atom,
R ₅ and R ₆ are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group.
[14" claim-type="Currently amended] The resin composition of Claim 13 which further contains a transition metal salt (D).
[15" claim-type="Currently amended] A resin composition containing a thermoplastic resin (B), a compatibilizer (C), and a transition metal salt (D), wherein the thermoplastic resin (B) has a unit represented by the following formula (I), and furthermore, a carbon-carbon double bond is 0.0001eq. It is contained in the ratio / g or more, and the resin composition whose number average molecular weights of the said thermoplastic resin (B) are 1000-50000.
Formula I

In Formula I,
R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R ₂ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group,
R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group which may be substituted, -COOR ₅ , -OCOR ₆ , a cyano group or a halogen atom,
R ₅ and R ₆ are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group.
[16" claim-type="Currently amended] The resin composition according to claim 14 or 15, wherein the resin composition contains a transition metal salt (D) in a proportion of 1 to 50000 ppm in terms of metal elements, based on the total weight of the thermoplastic resin (B) and the compatibilizer (C).
[17" claim-type="Currently amended] The resin composition according to any one of claims 14 to 16, wherein the transition metal salt (D) has at least one transition metal selected from the group consisting of iron, nickel, copper, manganese and cobalt.
[18" claim-type="Currently amended] 18. The thermoplastic according to any one of claims 1 to 17, wherein the compatibilizer (C) has at least one functional group selected from the group consisting of carboxyl groups, boronic acid groups, and boron-containing groups which can be converted to boronic acid groups in the presence of water. Resin composition which is resin.
[19" claim-type="Currently amended] The resin composition according to any one of claims 1 to 18, wherein the thermoplastic resin (B) has an aromatic vinyl compound unit and a diene compound unit.
[20" claim-type="Currently amended] The resin composition according to claim 19, wherein the diene compound unit is at least one of an isoprene unit and a butadiene unit.
[21" claim-type="Currently amended] The resin composition according to claim 19 or 20, wherein the aromatic vinyl compound unit is a styrene unit.
[22" claim-type="Currently amended] The resin composition of any one of Claims 19-21 whose thermoplastic resin (B) is a block copolymer.
[23" claim-type="Currently amended] A multilayer structure comprising at least one layer made of the resin composition according to any one of claims 1 to 22.
[24" claim-type="Currently amended] The multilayer container which contains one or more layers of the resin composition of any one of Claims 1-22, and a thermoplastic polyester layer, respectively.
[25" claim-type="Currently amended] A cap formed by mounting a gasket made of the resin composition according to any one of claims 1 to 22.

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同族专利:

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公开号 | 公开日

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CA2389307A1|2002-03-07|

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AU779071B2|2005-01-06|

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US6822031B2|2004-11-23|

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KR100615842B1|2006-08-25|

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EP1314761A1|2003-05-28|

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CN1392893A|2003-01-22|

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DE60134153D1|2008-07-03|

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US20030018114A1|2003-01-23|

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EP1314761B9|2008-10-29|

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CN1207347C|2005-06-22|

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AU8259701A|2002-03-13|

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EP1314761B1|2008-05-21|

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AT396234T|2008-06-15|

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EP1314761A4|2004-10-27|

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CA2389307C|2008-12-30|

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WO2002018496A1|2002-03-07|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2000-09-01|Priority to JP2000266185

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2000-09-01|Priority to JPJP-P-2000-00266184

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2000-09-01|Priority to JPJP-P-2000-00266185

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2000-09-01|Priority to JP2000266184

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2001-08-31|Application filed by 나카무라 하사오, 가부시키가이샤 구라레

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2002-06-21|Publication of KR20020047313A

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2006-08-25|Application granted

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2006-08-25|Publication of KR100615842B1

优先权:

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申请号 | 申请日 | 专利标题

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JP2000266185|2000-09-01|

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JPJP-P-2000-00266184|2000-09-01|

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JPJP-P-2000-00266185|2000-09-01|

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JP2000266184|2000-09-01|