JPH06107872A - Adhesive resin composition and laminate prepared by using same - Google Patents

Abstract

PURPOSE:To obtain the title composition useful for obtaining a laminate of excellent heat resistance by mixing a specified terpolymer with a polyamide resin in a specified ratio. CONSTITUTION:The composition comprises 60-95wt.% ethylene/alkyl alpha,beta-unsaturated carboxylate/maleic anhydride terpolymer, desirably one comprising 40-90wt.% repeating units derived from ethylene, 55-5wt.% repeating units derived from alkyl alpha,beta-unsaturated carboxylate and 0.1-10wt.% repeating units derived from maleic anhydride (e.g. ethylene/ethyl acrylate/maleic anhydride terpolymer) and 40-5wt.% polyamide resin (e.g. nylon 6).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a specific adhesive resin composition and a glass // resin composition layer or a glass // resin composition layer // polyamide resin layer or matrix using the resin composition. The present invention relates to a laminate comprising a multiphase thermoplastic resin composition layer whose phase is a polyamide resin.

[0002]

2. Description of the Related Art Polarity has been improved by graft-modifying a polyolefin typified by polyethylene or polypropylene with an unsaturated carboxylic acid such as acrylic acid or maleic anhydride or its anhydride. A method of introducing a group to impart adhesiveness to a substrate such as metal, glass, polar polymer and polyolefin is known (for example, JP-B-37-18392 and JP-B-52-32654). ). Also known is a method of imparting adhesiveness by copolymerizing an α-olefin typified by ethylene and a polar monomer such as glycidyl (meth) acrylic acid ester (for example, Japanese Patent Publication No. 46-27527).
JP-A-48-11388, etc.). A laminate of a copolymer of ethylene and maleic anhydride and a polyamide has been proposed (for example, JP-A-47-15486), and a copolymer of ethylene and maleic anhydride and an elastomer such as polyisobutylene. It is known that the addition of the compound improves the adhesion with the polyamide resin. However, these conventional methods are not satisfactory in heat resistance adhesiveness or adhesive strength in low temperature adhesion and are not satisfactory.

[0003]

In view of such circumstances, the present inventors have made a resin composition for adhesion, and further a glass layer // resin composition layer using the resin composition for adhesion, or a glass layer //
As a result of diligent examination of heat-resistant adhesiveness between layers of a laminate composed of a resin composition layer // thermoplastic resin layer and adhesive strength at low temperature adhesion, a specific adhesive resin composition was found and further The present invention has been completed by discovering that a laminate constituted by using a resin composition has improved adhesiveness between layers and has good heat resistance.

That is, the present invention provides (1) ethylene-
An adhesive resin composition comprising 60 to 95% by weight of an α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer and (2) 40 to 5% by weight of a polyamide resin.

Further, the present invention provides a laminate comprising the following (A) and (B). (A) glass layer, (B) (1) ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer 60 to 95% by weight, (2) polyamide resin 40 to 5% by weight A resin composition layer consisting of. Furthermore, the present invention provides a laminate comprising the following (A), (B) and (C). (A) glass layer, (B) (1) ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer 60 to 95% by weight, (2) polyamide resin 40 to 5% by weight (C) (1) a polyamide resin layer or (2) a multiphase thermoplastic resin composition layer in which the matrix phase is a polyamide resin.

The present invention will be described in detail below. One of the features of the present invention is a novel adhesive resin composition. Further, another feature of the present invention is that the adhesive resin composition layer has a glass layer and a polyamide resin layer or a matrix phase, with a laminate in which a glass layer is laminated, or the adhesive resin composition layer. And a multi-phase thermoplastic resin composition layer which is a polyamide resin, in a laminated body.

The adhesive resin composition of the present invention comprises (1) 60 to 95% by weight of ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer and (2)
A resin composition comprising 40 to 5% by weight of a polyamide resin.

(1) When the content of the ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer is less than 60% by weight, the adhesive strength at low temperature adhesion is lowered to 95% by weight. If it exceeds%, the heat-resistant adhesiveness is not sufficient. (2) When the polyamide resin is out of the range of 40 to 5% by weight, the adhesiveness is lowered.

(1) Ethylene-α, β- used in the present invention
The unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer is a copolymer produced by high pressure radical copolymerization. The α, β-unsaturated carboxylic acid alkyl ester is an unsaturated carboxylic acid having 3 to 8 carbon atoms, for example, an alkyl ester such as acrylic acid or methacrylic acid, and specific examples thereof include methyl acrylate and acrylic acid. Ethyl acid, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-acrylate
Butyl, isobutyl acrylate, methyl methacrylate,
Examples thereof include ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate and the like. Of these, methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are particularly preferable. These comonomers may be used alone or in combination of two or more.

The content of the α, β-unsaturated carboxylic acid alkyl ester in the ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer used in the present invention is not particularly limited. No, but preferably 5
˜55 wt%. When the content of the α, β-unsaturated carboxylic acid alkyl ester is lower than 5% by weight, the effect of improving the adhesiveness is small, while when it exceeds 55% by weight, the adhesive strength is sufficient but the production cost increases. .

The content of maleic anhydride in the ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer used in the present invention is not particularly limited, but is preferably 0. It is 1 to 10% by weight. When the content of the maleic anhydride is less than 0.1% by weight, the effect of improving the adhesiveness is small, while when it exceeds 10% by weight,
Adhesive strength is sufficient, but manufacturing cost increases.

The ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer used in the present invention has an ethylene unit content of 40 to 90% by weight and an α, β-unsaturated carboxylic acid alkyl ester unit 55. Copolymers consisting of ˜5% by weight and maleic anhydride units 0.1 to 10% by weight are preferred.

Used in the adhesive resin composition of the present invention (2)
As the polyamide resin, for example, various polyamides obtained by polycondensation of a lactam having 3 or more membered rings, a polymerizable ω-amino acid, a dibasic acid and a diamine can be used. Specifically, polymers such as ε-caprolactam, aminocaproic acid, enantolactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, or butanediamine, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylene. Polymers obtained by polycondensing diamines such as diamine and metaxylenediamine with dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid and glutaric acid, or copolymers thereof Is mentioned. Specific examples include polyamide-6, polyamide-66, polyamide-6.10, and polyamide-1.
1, aliphatic polyamides such as polyamide-12 and polyamide-6 · 12, polyhexamethylenediamine terephthalamide, polyhexamethylenediamine isophthalamide, aromatic polyamides such as xylene group-containing polyamide, and the like. The (2) polyamide resin used in the present invention is a mixture of one or more of these,
Alternatively, it can be used as a copolymer.

The laminate of the present invention comprises a laminate comprising (A) a glass layer and (B) a resin composition layer, or (B) a resin composition layer and (A) a glass layer and (C) a polyamide. It is a laminate in which a resin layer or a multiphase thermoplastic resin composition layer in which the matrix phase is a polyamide resin is laminated.

The (A) layer constituting the laminate of the present invention is not particularly limited as long as it is glass. For the layer (B) constituting the laminate of the present invention, the above-mentioned adhesive resin composition of the present invention can be used. The resin composition layer is a composition layer composed of (1) ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer and (2) polyamide resin. Constituting the laminate of the present invention (C)
The layer is (1) a polyamide resin layer or (2) a multi-phase thermoplastic resin composition layer in which the matrix layer is a polyamide resin. The polyamide resin used as the component (C) of the present invention may be the same as the polyamide resin used as a component of the layer (B). The multiphase thermoplastic resin composition layer in which the matrix layer used as the (C) layer component of the present invention is a polyamide resin is a composition comprising a polyamide resin and a resin selected from, for example, polyphenylene ether, polypropylene, ABS resin and the like. Can be mentioned. Examples of the polyamide resin include polyamide-6 and polyamide-66.
Etc. can usually be used.

A resin composition comprising a polyamide resin and a polyphenylene ether originally has a poor affinity for these resins, and therefore, even if they are melt-kneaded at the same time, the polyphenylene ether particles are dispersed only in a particle size of about 10 μm or more. However, since it has a drawback that it exhibits extremely low mechanical properties, a compatibility improver is blended.

Examples of the compatibilizer include the following a),
At least one compound selected from the group of b), c) and d) can be mentioned. a) In the molecule, a) carbon-carbon double bond or carbon-
Having a carbon triple bond and a) a carboxyl group, an acid anhydride group, an amino group, an acid amide group, an imide group, an epoxy group, a carboxylic acid ester group, an isocyanate group, a methylol group, a group having an oxazoline ring, or a hydroxyl group at the same time. It is a compound. Specific compounds include maleic acid, maleic anhydride, fumaric acid, unsaturated amines, glycidyl methacrylate, and the like (JP-A-56-56).
26913, and JP-A-56-49753).

B) Saturated aliphatic polycarboxylic acids and derivatives thereof represented by the following general formula (i). (R ₁ O) _m R (COOR ₂ ) _n (CONR ₃ R ₄ ) _s (i) (where R is a linear or branched aliphatic hydrocarbon having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms). R ₁ represents hydrogen, an alkyl group, an aryl group, an acyl group or a carbonyldioxy group, preferably hydrogen, and R ₂ represents hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group. Represents an alkyl group having 1 to 10 carbon atoms, R ₃ and R ₄ represent hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a carbon number. Represents an alkyl group of 1 to 4 m = 1 n + s: an integer of 2 or more, preferably 2 or 3. n, s: represents an integer of 0. (R ₁ O) represents an α-position of a carbonyl group or Positioned in beta There are 2 to 6 carbons between at least two carbonyl groups). Specific compounds include ester compounds of saturated aliphatic polycarboxylic acids, amide compounds, anhydrides, hydrates and salts. To be Examples of the saturated aliphatic polycarboxylic acid include citric acid, malic acid, agaricinic acid and the like (see Japanese Patent Publication No. 61-502195).

C) A compound represented by the following general formula (ii). (I) -Z- (II) (ii) (wherein (I) is at least formula (X-CO) [wherein X is F, Cl, Br, I, OH, OR or -O-C].
O-R, R is hydrogen, an alkyl group or an aryl group], (II) is at least a carboxylic acid, an acid anhydride group, an acid amide group, an imide group, a carboxylic acid ester group, an amino group or Represents a hydroxyl group. The groups (I) and (II) are covalently bonded via a bond Z which is a divalent hydrocarbon. ) Examples of the compound represented by the above general formula (ii) include chloroformyl succinic anhydride, chloroethanoyl succinic anhydride, trimellitic anhydride acid chloride, trimellitic anhydride acetic anhydride, and terephthalic acid chloride. Etc.

D) In the molecular structure: a) at least one silicon atom bonded to a carbon atom via a bridge of oxygen and a) at least an ethylenic carbon-carbon double bond or carbon-carbon triple bond and / or Alternatively, it is a silane compound having both an amino group and a functional group selected from a mercapto group, the functional group having no silicon atom bonded. Examples of the silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N- (βaminoethyl)-. Examples thereof include aminopropyltrimethoxysilane, N- (βaminoethyl) -aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane and γ-mercaptomethylethoxysilane.

The compatibility improver used in the present invention is not limited to the compounds exemplified here, and may be any compound used for the purpose of improving the compatibility of the polyamide resin and the polyphenylene ether, and a single compound or a plurality of compounds may be used. The compatibility improver may be used at the same time. Further, a radical initiator may be used together when the compatibility improver is blended. These resin compositions are useful resin compositions in which the weaknesses of the two-component resins, for example, the poor processability and low solvent resistance of polyphenylene ether, and the low heat resistance and high water absorption of polyamide resins have been improved. These resin compositions use a polyamide resin as a matrix to ensure processability. The resin composition composed of the polyamide resin and the polyphenylene ether comprises 100 to 30 parts by weight of the polyamide resin and 0 to 70 parts by weight of the polyphenylene ether. Further, these compatibility improvers are 0 to 30 parts by weight based on 100 parts by weight of the total of the polyamide resin and the polyphenylene ether,
It is preferably blended in an amount of 0.05 to 25 parts by weight.

A resin composition comprising a polyamide resin and polypropylene is a composition in which the weaknesses of the two-component resins, for example, the heat resistance and paintability of polypropylene, the water resistance, chemical resistance, and impact resistance of polyamide resin are improved. is there. These resin compositions use a polyamide resin as a matrix in order to ensure heat resistance. A resin composition composed of a polyamide resin and polypropylene is polyamide resin 100 to 3
0 parts by weight and 0 to 70 parts by weight of polypropylene. Further, these compatibility improvers are blended in an amount of 0 to 30 parts by weight, preferably 0.05 to 25 parts by weight, based on 100 parts by weight of the total of the polyamide resin and polypropylene.

A resin composition composed of a polyamide resin and ABS takes advantage of the heat resistance and oil resistance of the polyamide resin, and has the drawbacks of improved impact resistance and hygroscopicity by ABS and further reduced molding shrinkage. It is a feature. The resin composition composed of polyamide resin and ABS comprises 100 to 30 parts by weight of polyamide resin and 0 to 70 parts by weight of ABS. Further, these compatibility improvers are blended in an amount of 0 to 30 parts by weight, preferably 0.05 to 25 parts by weight, based on 100 parts by weight of the total of the polyamide resin and ABS.

The method for confirming that the matrix phase of these resin compositions is a polyamide resin is a method using a transmission electron microscope. An observation sample can be prepared by cutting out an ultrathin section using an ultramicrotome and immersing it in a phosphotungstic acid solution to dye the polyamide resin phase.

The method for producing the laminate of the present invention is not particularly limited, and its purpose is, for example, a thermocompression bonding method, an extrusion coating method, a dry laminating method, a powder coating method, or a combination thereof. Applied accordingly. In this case, it is also effective to use a surface-treated glass as a substrate in order to improve the adhesiveness with glass, and for example, a silane coupling agent or the like can be applied to the glass surface for the purpose of improving water-resistant adhesiveness. .

[0026]

As described above in detail, by laminating the adhesive resin composition of the present invention on the glass layer, or the multi-phase thermoplastic resin in which the glass layer and the polyamide layer or the matrix phase is a polyamide resin. By using an adhesive layer between the resin composition layers, it is possible to increase the adhesive strength between the layers and provide a laminate having improved heat resistant adhesiveness. In particular, blending a polyamide resin as one component of the adhesive resin composition improves the adhesive strength by thermocompression bonding at a temperature much lower than the melting point of the polyamide resin, which is an unexpected effect. Moreover, since the bonding can be performed in a short contact time, the working efficiency and working environment can be improved. Further, the laminate of the present invention can be used for applications requiring heat resistance such as automobile parts, construction parts, and electric equipment parts.

[0027]

The present invention will be described below with reference to examples, but the present invention is not limited thereto. 1. (B) Raw Material of Resin Composition for Adhesion In Examples and Comparative Examples, (1) ethylene-α, β
-Unsaturated carboxylic acid alkyl ester-Maleic anhydride terpolymer (hereinafter abbreviated as ethylene copolymer),
(2) The following materials were used as the polyamide resin. (1) Ethylene copolymer Bondine TX8030 Ethylene / ethyl acrylate / maleic anhydride = 85/1
1.5 / 3.5% by weight, MFR = 3.0 g / 10 minutes (190 ° C, 2160 g) (2) Polyamide resin Polyamide-6, (manufactured by Unitika) (relative viscosity = 2.17dl
/ g) A1022S Polyamide-6, (made by Unitika) (relative viscosity = 3.4 dl
/ g) A1030BRT

2. Substrate Layers (A) and (C) In the examples and comparative examples, the following substances were used as the substrate layers (A) and (C), respectively. (A) Glass A slide glass was used. (C) Polyamide resin Rayfan # 1401 100 μ PA-6 film (manufactured by Toray Synthetic Film) Resin composition consisting of polyamide resin and polyphenylene ether (PPE) A-1 PPE / PA-6 / MAH / GF = 35/35 /0.5/30 parts by weight Injection molded sheet 2mm thickness A-2 PPE / PA-66 / MAH / GF = 35/35 / 0.5 / 30 parts by weight Injection molded sheet 2mm thickness A-3 PPE / PA-6 / SBS / MAH = 40/50/10 / 0.3 parts by weight Injection molded sheet 2mm Thickness A-1 and A-2 are polyamide resin and polyphenylene ether and maleic anhydride (MAH) as a compatibility improver
Further, a composition obtained by melt-kneading glass fibers (GF), A-3 is a composition obtained by adding a styrene-butadiene-styrene block copolymer (SBS) as an impact resistance improver, and is a polyamide resin matrix. It is a multiphase structure in which polyphenylene ether is finely dispersed. The grain structure of the multiphase structure was observed by making a photograph using a transmission electron microscope. The observation sample was prepared by cutting an ultrathin section from an injection-molded sheet using an ultramicrotome, immersing it in a phosphotungstic acid solution, and dyeing the polyamide phase.

3. Adhesion evaluation method (1) Adhesion test Glass /// resin composition laminate Structure of laminate Glass // resin composition layer (150 μ film) Adhesion conditions Heat seal tester 100 ° C × pressure 1 kg / cm ² × pressurization Time 5 seconds Peeling condition 180 ° peeling Under 23 ° C, peeling speed 100mm / min against polyamide substrate Composition of laminate PA-6 film // Resin composition layer (50μ film) // PA-6 film Adhesion condition Heat seal tester 120 ℃ × pressure 3 kg / cm ² × pressurization time 3 seconds Peeling condition Shear peeling at a predetermined temperature, peeling speed 10 mm / min Polyamide resin composition Laminated composition PA composition // Resin composition layer (150μ film) // PA-6 film First, a film made of a resin composition and a PA-6 film are heat-sealed at 190 ° C and a pressure of 3 kg / cm.
^{It was} thermocompression-bonded under the condition of ² × pressurization time of 3 seconds and then bonded to the polyamide resin composition. Adhesion conditions Heat seal tester 120 ° C × pressure 3 kg / cm ² × pressurization time 3 seconds Peeling condition Shear peeling at a predetermined temperature, peeling speed 10 mm / min Glass // resin composition // polyamide substrate or polyamide resin composition laminate Laminate Body composition Glass // Resin composition layer (150μ film) // PA-6 film is polyamide resin composition Adhesion condition Press 160 ℃ × Pressure 5 kg / cm ² × Pressing time 3 minutes Peeling condition Shear peeling Under specified temperature, Peeling speed 10 mm / min

Examples 1 to 3 Using a 30 mmφ twin-screw extruder equipped with a vent device, a preset temperature of 260
The ethylene copolymer and the polyamide resin shown in Table 1 were melt-kneaded at 0 ° C. to obtain an adhesive resin composition. After the adhesive resin composition thus obtained was dried, the film was molded at a preset temperature of 260 ° C. using a 20 mmφT die film molding machine to obtain films with thicknesses of 50 μ and 150 μ, respectively. Using the film, a laminate was produced and the adhesiveness was evaluated. The evaluation results are shown in Table 1.

Comparative Example 1 The ethylene copolymer TX8030 was molded into a film at a preset temperature of 260 ° C. using a 20 mmφT die film molding machine to obtain a film having a thickness of 50 μ and a film having a thickness of 150 μ, respectively. Using the film, a laminate was produced and the adhesiveness was evaluated.
The evaluation results are shown in Table 1.

[0032]

[Table 1]

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Claims (12)

[Claims] (1) Ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer 60
~ 95 wt% and (2) polyamide resin 40-5 wt%
An adhesive resin composition comprising: 2. An ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer having an ethylene unit content of 40 to 90% by weight and an α, β-unsaturated carboxylic acid alkyl ester unit content of 55 to 5 2. A copolymer comprising 1% by weight and 0.1 to 10% by weight of maleic anhydride unit.
The adhesive resin composition described. 3. A laminate comprising the following (A) and (B). (A) glass layer, (B) (1) ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer 60 to 95% by weight, (2) polyamide resin 40 to 5% by weight A resin composition layer consisting of. 4. A laminate comprising the following (A), (B) and (C). (A) glass layer, (B) (1) ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer 60 to 95% by weight, (2) polyamide resin 40 to 5% by weight (C) (1) a polyamide resin layer or (2) a multiphase thermoplastic resin composition layer in which the matrix phase is a polyamide resin. 5. An ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer having an ethylene unit content of 40 to 90% by weight and an α, β-unsaturated carboxylic acid alkyl ester unit content of 55 to 5 4. A copolymer comprising 0.1% by weight of maleic anhydride unit and 0.1% by weight of maleic anhydride unit.
Or the laminated body of 4 above. 6. The laminate according to claim 4, wherein the multiphase thermoplastic resin composition whose matrix phase is a polyamide resin is a resin composition comprising a polyamide resin and polyphenylene ether. 7. The laminate according to claim 4, wherein the multiphase thermoplastic resin composition whose matrix phase is a polyamide resin is a resin composition comprising a polyamide resin, polyphenylene ether and glass fibers. 8. The laminate according to claim 6, wherein the polyamide resin (C) (2) is polyamide-6. 9. The laminate according to claim 6, wherein the polyamide resin (C) (2) is polyamide-66. 10. The laminate according to claim 6, wherein the resin composition comprising a polyamide resin and polyphenylene ether is a resin composition comprising a polyamide resin, polyphenylene ether and a compatibility improver. 11. The laminate according to claim 4, wherein the multiphase thermoplastic resin composition whose matrix phase is a polyamide resin is a resin composition comprising a polyamide resin and polypropylene. 12. The laminate according to claim 4, wherein the multiphase thermoplastic resin composition whose matrix phase is a polyamide resin is a resin composition comprising a polyamide resin and ABS.