JP3245992B2 - Adhesive resin composition and laminate using the composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass using a specific adhesive resin composition // a resin composition layer // a polyamide resin layer or a multiphase thermoplastic resin composition layer in which the matrix phase is a polyamide resin. The present invention relates to a laminate comprising:

[0002]

2. Description of the Related Art Conventionally, a polyolefin represented by polyethylene or polypropylene is polarized by graft modification with an unsaturated carboxylic acid such as acrylic acid or maleic anhydride or an anhydride thereof. A method of introducing a group to impart adhesiveness to a substrate such as a metal, glass, a polar polymer, and a polyolefin is known (for example, Japanese Patent Publication No. 37-18392, Japanese Patent Publication No. 52-32654, etc.). ). Also known is a method of imparting adhesion by copolymerizing an α-olefin represented by ethylene and a polar monomer such as glycidyl (meth) acrylate (for example, Japanese Patent Publication No. 46-27527).
JP, 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 has been added to an elastomer such as polyisobutylene. Is known to improve the adhesiveness to a polyamide resin. However, these conventional methods are insufficient in heat resistance and low-temperature adhesion and are not satisfactory.

[0003]

SUMMARY OF THE INVENTION In view of the above circumstances, the present inventors have proposed a method for forming a laminate comprising a glass layer using an adhesive resin composition, a resin composition layer, and a thermoplastic resin layer. as a result of intensive studies for adhesion of a heat adhesiveness and low temperature adhesion of the interlayer, the laminate constituted by using a specific adhesive resin composition to improve the adhesion between the layers is good heat-resistant That is, the present invention has been completed.

[0004]

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

Hereinafter, the present invention will be described in detail. Of the present invention
The feature is a laminate in which a glass layer and a polyamide resin layer or a multi-phase thermoplastic resin composition layer in which a matrix phase is a polyamide resin are laminated via an adhesive resin composition layer .

[0007] The adhesive resin composition used in the present invention comprises:
(1) Ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer 60 to 95% by weight
And (2) 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 bonding is reduced, and the weight is 95%. %, The heat resistant adhesiveness is not sufficient. (2) When the amount of the polyamide resin is out of the range of 40 to 5% by weight, the adhesiveness is reduced.

(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 and methacrylic acid. Specific examples thereof include methyl acrylate and acrylic acid. Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-acrylate
Butyl, isobutyl acrylate, methyl methacrylate,
Examples include ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and isobutyl methacrylate. Of these, methyl acrylate, ethyl acrylate, n-butyl acrylate and methyl methacrylate are particularly preferred. These comonomers can be used alone or in combination of two or more.

The content of the α, β-unsaturated carboxylic acid alkyl ester of 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% by weight. If the content of the α, β-unsaturated carboxylic acid alkyl ester is less than 5% by weight, the effect of improving the adhesiveness is small. .

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 0.1%. 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.
Adhesive strength is sufficient, but manufacturing costs increase.

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 comprising -5% by weight and 0.1-10% by weight of maleic anhydride units are preferred.

The (2) polyamide resin used in the adhesive resin composition used in the present invention is obtained, for example, by polycondensation of a lactam having three or more ring members, a polymerizable ω-amino acid, a dibasic acid and a diamine. Various polyamides can be used. Specifically, polymers such as ε-caprolactam, aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, or butanediamine, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylene Polymers obtained by polycondensing diamines such as diamine and meta-xylene diamine with dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid and glutaric acid, or copolymers thereof Is mentioned. As a specific example, polyamide-
6, polyamide-66, polyamide-6.10, polyamide-11, polyamide-12, polyamide-6.12
And aromatic polyamides such as polyhexamethylene diamine terephthalamide, polyhexamethylene diamine isophthalamide, and xylene group-containing polyamide. As the (2) polyamide resin used in the present invention, one or more of these may be used as a mixture or as a copolymer.

The laminate of the present invention comprises: (B) a glass layer via a resin composition layer; and (C) a polyamide resin layer or a multiphase thermoplastic resin composition layer in which the matrix phase is a polyamide resin. Are laminated.

The layer (A) constituting the laminate of the present invention is not particularly limited as long as it is glass. The layer (B) constituting the laminate of the present invention can use the above-mentioned adhesive resin composition of the present invention. The resin composition layer is a composition layer comprising (1) an ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer and (2) a 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 a component of the layer (C) of the present invention may be the same as the polyamide resin used as a component of the layer (B). The multi-phase thermoplastic resin composition layer in which the matrix layer used as the layer component (C) 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. No. Examples of the polyamide resin include polyamide-6 and polyamide-66.
Etc. can usually be used.

A resin composition comprising a polyamide resin and polyphenylene ether originally has poor affinity, so that even when melt-kneaded, polyphenylene ether particles are dispersed only with a particle diameter of about 10 μ or more. However, they have the drawback that they exhibit only extremely low mechanical properties, so that a compatibility improver is incorporated.

Examples of the compatibilizer include the following a),
At least one compound selected from the group of b), c) and d) is included. a) In a molecule, a) a carbon-carbon double bond or
It has 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 ester group, an isocyanate group, a methylol group, a group having an oxazoline ring, or a hydroxyl group at the same time. Compound. Specific compounds include maleic acid, maleic anhydride, fumaric acid, unsaturated amines, glycidyl methacrylate and the like (Japanese Patent Application Laid-open No.
26913, and JP-A-56-49753).

B) Saturated aliphatic polycarboxylic acids represented by the following general formula (i) and derivatives thereof. (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 a hydrogen, an alkyl group, an aryl group, an acyl group or a carbonyldioxy group, preferably represents a hydrogen R ₂ represents a hydrogen, an alkyl group or an aryl group having 1 to 20 carbon atoms, preferably Represents an alkyl group having 1 to 10 carbon atoms R ₃ and R ₄ represent hydrogen, an alkyl group or an aryl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. M = 1 n + s: an integer of 2 or more, preferably 2 or 3. n, s: an integer of 0 or more (R ₁ O) represents the α-position of the carbonyl group or Beta position And 2 to 6 carbon atoms are present between at least two carbonyl groups. Specific examples include saturated aliphatic polycarboxylic acid ester compounds, amide compounds, anhydrides, hydrates and salts. Can be Examples of the saturated aliphatic polycarboxylic acid include citric acid, malic acid, agaric acid and the like (see Japanese Patent Application Laid-Open No. 61-502195).

C) A compound represented by the following general formula (ii). (I) -Z- (II) (ii) (where (I) is at least the formula (X-CO) wherein X is F, Cl, Br, I, OH, OR or -OC
Wherein 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 ester group, an amino group or Represents a hydroxyl group. The groups (I) and (II) have a covalent bond via a bond Z which is a divalent hydrocarbon. Examples of the compound represented by the general formula (ii) include chloroformyl succinic anhydride, chloroethanoyl succinic anhydride, trimellitic anhydride chloride, trimellitic anhydride acetic anhydride, and terephthalic chloride. And the like.

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

The compatibility improver used in the present invention is not limited to the compounds exemplified herein, but may be any compound used for the purpose of improving the compatibility between the polyamide resin and the polyphenylene ether. May be used at the same time. When the compatibility improver is compounded, a radical initiator may be used in combination. These resin compositions are useful resin compositions in which the weak points of the two-component resin, for example, the difficulty in processing and low solvent resistance of polyphenylene ether, and the low heat resistance and high water absorption of polyamide resins are improved. These resin compositions use a polyamide resin as a matrix to ensure processability. The resin composition comprising a polyamide resin and polyphenylene ether is composed of 100 to 30 parts by weight of a polyamide resin and 0 to 70 parts by weight of a 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.
Preferably 0.05 to 25 parts by weight is blended.

A resin composition comprising a polyamide resin and polypropylene is a composition in which the weaknesses of both 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 to ensure heat resistance. The resin composition comprising a polyamide resin and polypropylene is a polyamide resin 100 to 3
0 parts by weight and 0 to 70 parts by weight of polypropylene. These compatibility improvers are added 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 the polypropylene.

The resin composition comprising a polyamide resin and ABS can make use of the heat resistance and oil resistance of the polyamide resin, improve the impact resistance and moisture absorption, which are disadvantages, by ABS, and reduce the molding shrinkage. It is a feature. The resin composition comprising the polyamide resin and the ABS comprises 100 to 30 parts by weight of the polyamide resin and 0 to 70 parts by weight of the ABS. These compatibility improvers are added 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 the ABS.

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

The method for producing the laminate of the present invention is not particularly limited, and examples thereof include a thermocompression bonding method, an extrusion coating method, a dry laminating method, a powder coating method, and a combination thereof. Applied accordingly. In this case, it is also effective to use a surface-treated glass as a base material in order to increase the adhesiveness with the glass. 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]

Effect of the Invention] As described above in detail, et used in the present invention
The adhesive resin composition to be used is a glass layer and an adhesive layer between layers of a multi-phase thermoplastic resin composition in which the polyamide layer or the matrix phase is a polyamide resin, thereby increasing the adhesive strength between the layers and improving the heat resistance. Can be provided. In particular, it is an unpredictable effect that the addition of the polyamide resin as one component of the adhesive resin composition has improved the adhesive strength by thermocompression bonding at a temperature much lower than the melting point of the polyamide resin. Moreover, since the bonding can be performed in a short contact time, the working efficiency and the working environment can be improved. Further, the laminate of the present invention is an automobile part,
It can be used for applications requiring heat resistance, such as architectural and electrical equipment parts.

[0027]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. 1. (B) Raw Material of Adhesive Resin Composition 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 were used as the polyamide resins. (1) Ethylene copolymer Bondyne TX8030 Ethylene / ethyl acrylate / maleic anhydride = 85/1
1.5 / 3.5 wt%, MFR = 3.0 g / 10 min (190 ° C., 2160 g) (2) Polyamide resin Polyamide-6 (manufactured by Unitika) (relative viscosity = 2.17 dl)
/ 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 were used as the substrate layers (A) and (C), respectively. (A) Glass A slide glass was used. (C) Polyamide resin Leifan # 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, polyphenylene ether and maleic anhydride (MAH) as a compatibility improver
A-3 is a composition obtained by melting and kneading glass fiber (GF), and A-3 is a composition obtained by adding a styrene-butadiene-styrene block copolymer (SBS) as an impact resistance improver. It is a multiphase structure in which polyphenylene ether is finely dispersed. The particle structure of the multiphase structure was observed by making a photograph using a transmission electron microscope. The observation sample was prepared by cutting out an ultrathin section from an injection-molded sheet using an ultramicrotome, immersing the section in a phosphotungstic acid solution, and dyeing the polyamide phase.

3. Evaluation method of adhesion (1) Adhesion test Glass // construction glass // resin composition layer of the resin composition laminate stack (0.99 mu Film) bonding conditions heat seal tester 100 ° C. × pressure 1 kg / cm ² × pressure Time 5 seconds Peeling condition 180 ° peeling 23 ° C, peeling speed 100mm / min vs. polyamide base laminate composition 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 Peeling speed 10mm / min at predetermined temperature vs. polyamide resin composition Laminate composition PA composition // resin composition layer (150μ film) // PA-6 Film First, a film composed of a resin composition and a PA-6 film were heated at 190 ° C. × 3 kg / cm by a heat seal tester.
Thermocompression bonding was performed under the conditions of ² × pressurizing time of 3 seconds, and then the resultant was bonded to the polyamide resin composition. Adhesion conditions Heat seal tester 120 ° C × pressure 3 kg / cm ² × pressurization time 3 seconds Peeling conditions Shear peeling Peeling speed 10mm / min at a predetermined temperature Glass // Resin composition // Polyamide substrate or polyamide resin composition laminate Composition of body Glass // resin composition layer (150μ film) // PA-6 film is polyamide resin composition Adhesion condition Press 160 ° C × 5kg / cm ² × Pressure time 3min. Peeling condition Shear peeling Peeling speed 10mm / min

Examples 1 to 3 Using a 30 mmφ twin-screw extruder equipped with a vent device, a set temperature of 260
At 0 ° C., the ethylene copolymer and the polyamide resin shown in Table 1 were melt-kneaded to obtain an adhesive resin composition. After drying the adhesive resin composition thus obtained, films were formed at a set temperature of 260 ° C. using a 20 mmφT die film forming machine to obtain films having a thickness of 50 μ and 150 μ, respectively. Laminates were produced using the films, and the adhesion was evaluated. Table 1 shows the evaluation results.

COMPARATIVE EXAMPLE 1 A film of TX8030, which is an ethylene copolymer, was formed at a set temperature of 260 ° C. using a 20 mmφT die film forming machine to obtain films having a thickness of 50 μm and 150 μm, respectively. Laminates were produced using the films, and the adhesion was evaluated.
Table 1 shows the evaluation results.

[0032]

[Table 1]

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ identification code FI C08L 77:00) C08L 77:00) (56) References JP-A-61-151254 (JP, A) JP-A-5-77354 (JP, A) JP-A-6-106568 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 17/10 B32B 27/08 C08L 23/00-23/36 C09J 123 / 00-123/36 C08L 77/00-77/12

Claims (9)

(57) [Claims] 1. A laminate comprising the following (A), (B) and (C). (A) a glass layer, (B) (1) 60 to 95% by weight of an ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer, and (2) 40 to 5% by weight of a polyamide resin. (C) (1) a polyamide resin layer or (2) a multiphase thermoplastic resin composition layer in which the matrix phase is a polyamide resin. 2. An ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride terpolymer comprising 40 to 90% by weight of ethylene units and 55 to 5% of α, β-unsaturated carboxylic acid alkyl ester units. 2. A copolymer comprising 1 to 10% by weight of maleic anhydride units.
The laminate according to the above. 3. A multi-phase thermoplastic resin composition matrix phase is a polyamide resin laminate according to claim 1, wherein the resin composition comprising a polyamide resin and polyphenylene ether. 4. A multi-phase thermoplastic resin composition matrix phase is a polyamide resin laminate according to claim 1, wherein the resin composition comprising a polyamide resin and polyphenylene ether and fiberglass. 5. The laminate according to claim 3 , wherein the polyamide resin (C) (2) is polyamide-6. 6. The laminate according to claim 3 , wherein the polyamide resin of (C) (2) is polyamide-66. 7. The laminate according to claim 3 , 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. 8. multiphase thermoplastic composition matrix phase is a polyamide resin laminate according to claim 1, wherein the resin composition comprising a polyamide resin and polypropylene. 9. multiphase thermoplastic composition matrix phase is a polyamide resin laminate according to claim 1, wherein the resin composition comprising a polyamide resin and ABS.