• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    PURPOSE: A polyamide resin composition for the manufacture of a film is provided which can be processed as a film suitable to physical properties requested by the users of the film by maintaining the tenacity, surface characteristics and transparency of the film and improving a binding force to other resins. CONSTITUTION: A polyamide resin composition for the manufacture of a film is described which is characterized by adding a polyamide resin with 0.05 to 5% by weight of additives of the formula (A)NH2-(R1-NHCO-R2CONH)n-R1NH2, (D)HOOC-(R2-CONH-R1NHCO)m-R2COOH and (E)HOOC-(R2-CONH-R1NHCO)l-R2CONH-R1NH2. In formula, R1 is an alkyl group containing 6 to 12 of carbon, an aromatic group containing 6 to 12 of carbon, R2 is an alkyl group containing 2 to 36 of carbon, an unsaturated linear 6 to 36 of hydrocarbon, m, n are repeating units of 1 to 10, l is a repeating unit of 3 to 20. The film obtained by the resin composition has improved a coefficient of statical friction, tensile strength, and peeling strength and can be used as various uses.
    公开号:KR20000028038A
    申请号:KR1019980046161
    申请日:1998-10-30
    公开日:2000-05-15
    发明作者:오명환；박경남
    申请人:조정래；주식회사 효성；
    IPC主号:
    专利说明:

    Polyamide resin composition for film production
    The present invention relates to a polyamide resin composition for producing a film, and more particularly, to a polyamide resin composition for producing a film, which has excellent adhesive strength with other resins in film lamination and can be processed into a film suitable for the physical properties of a polyamide film user. It is about.
    Polyamide film is excellent in toughness, heat resistance, cold resistance, oil resistance, impact resistance, chemical resistance, pinhole resistance, gas barrier properties, and the like. Therefore, it is widely used in various applications such as packaging for livestock processed products such as ham and sausage, dairy products such as cheese and butter, processed products, retorot food, frozen food, liquid soup, and the like.
    Polyamide film is usually applied by lamination, coating or co-extrusion, such as polyethylene lamination, AI coating or PVDC coating. Polyamide films have excellent gas barrier properties, but are poor in water vapor barrier due to the water affinity of the amide groups due to their polyamide molecular structure. Therefore, it is usually used by laminating polyolefin or PVDC with excellent water vapor barrier properties. Therefore, after lamination, it requires a strong bonding force between nylon and other materials in three-way sealing, sterilization heat treatment, and consumer use in post-processing. In general, it is difficult to solve such a problem by adjusting only the physical properties of the polyamide film itself, and thus improvement has been required.
    An object of the present invention is to provide a resin composition for manufacturing a film that can be processed into a film suitable for the physical properties of the polyamide film user by improving the bonding strength with other resins while maintaining the toughness, surface properties, and transparency that the polyamide film should have. It is.
    The present invention is characterized in that an organic compound containing both an amine group and an acid group or both an amine group and an acid group is added to a polymer of polyamide.
    Hereinafter, the present invention will be described in detail.
    Compound (A) in which the sock end contains an amine group is a reactant of diesides (B) and an excess of diamines (C) such that the sock end is blocked with an amine group. The reaction product of diamines (C) and excess diesides (B) so as to be blocked, and the compound (E) which contains an amine group and an acidic group simultaneously equivalent reaction of diamines (C) and diesides (B) And reactants obtained by terminating the reaction at a conversion rate of less than 70%.
    Adhesion promoters (A), (D) and (E) compounds used in the present invention can be prepared as follows.
    (A) Adhesion Promoting Diamine:
    (x + y) NH 2 -R1-NH 2 + xHOOC-R2-COOH → NH 2- (R1-NHCO-R2CONH) n-R1NH 2
    (C) (B) (A)
    R <1> is a C2-C12 alkyl group and a C6-C12 aromatic group here
    R2: an alkyl group having 2 to 36 carbon atoms, 6 to 36 unsaturated linear hydrocarbons,
    6 to 36 unsaturated cyclic hydrocarbons
    x: mole number of dimer acid
    x + y: mole number of diamines (y is 1.3 to 3 times x)
    n: repeating unit of 1 to 10
    That is, after reacting (B) with excess (C) at a reaction temperature of 200 to 250 ° C. for 2 to 6 hours at a vacuum degree of 200 to 600 torr, the excess (C) is washed with water in a range of 30 to 50 ° C. to remove The final compound (A) is obtained.
    (D) Adhesion Promoting Diacid:
    aNH 2 -R1-NH 2 + (a + b) HOOC-R2-COOH → HOOC (R2-CONH-R1NHCO) m-R2COOH
    (C) (B) (D)
    R <1> is a C2-C12 alkyl group and a C6-C12 aromatic group here
    R2: a C2-C36 alkyl group, 6-36 unsaturated linear hydrocarbon.
    6 to 36 unsaturated cyclic hydrocarbons
    a: mole number of diamines
    a + b: mole number of dimer acid (b is 1.3 to 3 times a)
    m: repeating unit of 1 to 10
    That is, after reacting excess (B) with (C) at a reaction temperature of 200 to 250 ° C. for 2 to 6 hours in a vacuum range of 200 to 600 torr, the excess (B) is washed with ethanol in the range of 30 to 50 ° C. and removed. The final compound (D) is obtained.
    (E) Adhesion Promoter:
    cNH 2 -R1-NH 2 + cHOOC-R2-COOH → HOOC- (R2-CONH-R1NHCO) I-R2CONH-R1NH 2
    (C) (B) (E)
    R <1> is a C2-C12 alkyl group and a C6-C12 aromatic group here
    R2: C2-C36 alkyl group, 6-36 unsaturated linear hydrocarbon
    c: mole number of diamines and diesides
    I: repeating unit of 3 to 20
    That is, (C) and (B) were added to the reactor in an equivalent ratio, and the reaction was completed at a conversion rate of 50 to 70% while reacting for 2 to 6 hours at a reaction temperature of 200 to 250 ° C and a vacuum degree of 200 to 600 torr, and then 30 to 50 ° C. The first wash with water in the range followed by second wash with ethanol at 30-50 ° C. affords the unreacted compound (E).
    Generally, a polyamide film is urethane-based as an adhesive for lamination with polyolefins. Urethane-based adhesives can identify a role as a mechanism for inducing bonding of heterogeneous films by self-crosslinking by curing. However, since urethane-based adhesives do not have inherently compatibility with polyamides, peeling phenomenon occurs mainly during the heat treatment or reworking, in which the laminating adhesive portion is separated from the polyamide film. Therefore, in order to prevent this, there is a method of using an adhesive resin having excellent adhesive strength or improving bonding strength with the adhesive resin through modification of both matrix resins.
    In the present invention, a component containing a reactive group capable of reacting with the isocyanate group of the adhesive resin without adding a difference in polyamide and solubility parameter rather than a modification of the polyamide matrix resin of the polyamide resin composition is added. do.
    The resin composition for polyamide films can be used by adding inorganic fine particles such as silica, talc, and kaolin, which are known additives, and lubricants such as fatty acid amides.
    Polyamide resins that can be used in the present invention include copolymers based on nylon 6 and nylon 6 as main components. Examples of copolymers based on nylon 6 include 40-99.9% by weight of ε-caprolactam, hexamethylenediamine, 2-methylterenediamine, metaparaxylenediamine, terephthalic acid, isophthalic acid, adipic acid and 12-amino The polyamide copolymer obtained by melt-polymerizing 0.1-60 weight% of mixtures, such as a dodecanoic acid or lauryl lactam, is mentioned.
    In the present invention, when the reactive compound used as the adhesion strength enhancer of the polyamide resin is less than 0.05% by weight, the user may not achieve the desired level of physical property improvement. On the contrary, when the reactive compound is more than 5% by weight, the surface properties of the film may be deteriorated. The intrinsic properties of the film may be compromised. The compound used as the adhesion strength enhancer may be added through a polymerization process or a blending process of the matrix resin of the polyamide resin composition, but the physical properties of the matrix resin may be reduced by the reaction of the polymer during the polymerization process or the extrusion process. Therefore, the additive of the present invention advantageously uses a method of introducing a static mixer at the end of the extruder and using a side feeder to uniformly disperse the reaction with the polyamide matrix resin at the end of the extruder. Do.
    The resin composition for films produced by the above-described method can be molded into a film by a generally known T-die method or inflation method. For example, the chip is fed into an extruder through a hopper, heated to melt, extruded from an extrusion die, and then cooled and solidified to produce an unstretched fabric, which is then simultaneously co-ordinated in the advancing direction (MD) and width direction (TD) of the film. Alternatively, the film may be prepared by heat-setting after successive stretching.
    The polyamide resin composition for producing a film of the present invention may be produced by a film alone, or co-extruded with ethylene vinyl alcohol copolymer (EVOH) to further improve the gas barrier property of the final film according to a known method, or It can be made into a film by a method of coating polyvinylidene chloride (PVDC) having good gas barrier property.
    The biaxially stretched polyamide film prepared from the polyamide resin composition of the present invention and the laminate film prepared by laminating with other films have excellent surface properties, transparency, and adhesive strength with other resins to suit the user's requirements. It has the advantage of improved physical properties.
    Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are only for describing specific embodiments of the present invention, and the present invention is not limited to the following Examples.
    The physical property evaluation method of the film used in the present Example is as follows.
    (Assessment Methods)
    1. Transparency: According to ASTM D-1003, haze was measured using a haze meter manufactured by Nippon Electric Corporation.
    2. Friction coefficient: measured according to ASTM D-1894 using static friction coefficient measuring instrument at 20 ° C and 65% humidity.
    3. Tensile strength: in accordance with ASTM D-882 was measured using a universal tensile tester at 20 ℃, 65% relative humidity atmosphere.
    4. Peeling strength: in accordance with ASTM D-1876 was measured using a universal tensile tester at 23 ℃, relative humidity 50% atmosphere.
    (Example 1)
    Adhesion promoters A, D, and E were obtained by polymerization through condensation reaction with the composition shown in Table 1. Adhesion promoter A-1 was introduced into the nylon 6 molten resin at a temperature of 200% through a side feeder attached to a cold press, and passed through a static mixer to uniformly mix the adhesion promoter with nylon 6. Subsequently, the substrate was extruded downward at 250 ° C. using an annular die having a diameter of 400 mm, and quenched with water at 15 ° C. to obtain an unstretched film fabric.
    Pressurized gas was fed into the tube between two sets of nip rollers with different speeds and simultaneously biaxially stretched with MD / TD = 3 / 3.2 times to produce a film diameter of 700 mmφ and a thickness of 15 µm at a film surface temperature of 70 ° C. Phosphorus biaxially oriented film was prepared. Next, the stretched film is transferred to the heat setting tower through the guide roller, and then the low heat gas is fed into the film while the heat setting tower is 60 m in a tube state so that the film surface temperature is 70 ° C continuously. First heat setting and folding at 180 ° C. for 8 seconds while passing at the rate of per minute and folding, separating the films into two sheets, contacting each film with the second heat treatment roller, and second heat setting at 90 ° C. for 3 seconds, then winding up to the winder. The final polyamide film was prepared.
    The obtained polyamide film was coated with an adhesive and subjected to lamination with a polyethylene film to obtain a lamination film. At this time, the guide plate was installed at both ends of the film to prevent the adhesive from being coated so that it could be taken as a grip part during the evaluation of peeling. Evaluation of the properties of the single biaxially stretched nylon film and evaluation of the peeling properties of the laminator film are shown in Table 3 below.
    (Examples 2 to 4)
    A polyamide film was prepared under the same conditions and methods as in Example 1, except that the adhesion promoter in Example 1 was changed as shown in Table 2 with respect to nylon 6 resin, and the physical properties thereof were evaluated in Table 3 below. Shown together.
    (Comparative Examples 1 to 3)
    In Example 1, a polyamide film was prepared under the same conditions and methods as in Example 1 except that the components and composition of the adhesion promoter for nylon 6 resin were changed outside the scope of the present invention as shown in Table 2, and the physical properties thereof were evaluated. It is shown together in Table 3 below.
    divisionKindsA-1A-2DE Monomer content (% by weight)Hexamethylene diamine7003050 Ethylene diamine07000 C36 dimer acid (a)30307050 Melting temperature (℃)120110115130
    (a): Emery Industries Inc.
    divisionAdhesion Promoter ClassAdhesion Promoter Content (% by weight of total resin) Example 1A-10.1 Example 2A-20.2 Example 3D0.1 Example 4E0.1 Comparative Example 1A-10.01 Comparative Example 2A-16 Comparative Example 3No addition0
    Transparency (%)Static friction coefficient (μs)Tensile Strength (㎏ / ㎠)Peeling Strength (N / m) Example 12.50.502500650 Example 22.60.522450670 Example 32.50.522500600 Example 42.30.482600600 Comparative Example 12.50.602500450 Comparative Example 24.30.902350700 Comparative Example 32.50.502450450
    As can be seen by the above embodiment, the film produced by the resin composition of the present invention can be used in various applications to improve the physical properties such as transparency, static friction coefficient, tensile strength, peeling strength.
    权利要求:
    Claims (1)
    [1" claim-type="Currently amended] The polyamide resin composition for film production, wherein an additive (A, D, E) represented by the following formula is added to the polyamide resin in an amount of 0.05 to 5% by weight.
    (A) adhesion promoting diamine
    NH 2- (R1-NHCO-R2CONH) n-R1NH 2
    (D) Adhesion Promoting Dieside
    HOOC- (R2-CONH-R1NHCO) m-R2 COOH
    (E) adhesion promoter
    HOOC- (R2-CONH-RINHCO) I-R2 CONH-R1NH 2
    Here, R1: a C2-C12 alkyl group and a C6-C12 aromatic group.
    R2: a C2-C36 alkyl group, 6-36 unsaturated linear hydrocarbon.
    m, n: repeating unit of 1 to 10.
    I: repeating unit of 3 to 20.
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    同族专利:
    公开号 | 公开日
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-10-30|Application filed by 조정래, 주식회사 효성
    1998-10-30|Priority to KR1019980046161A
    2000-05-15|Publication of KR20000028038A
    优先权:
    申请号 | 申请日 | 专利标题
    KR1019980046161A|KR20000028038A|1998-10-30|1998-10-30|Polyamide resin composition for manufacture of film|
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