WO2003066771A1 - Adhesive resin composition and use thereof - Google Patents

Abstract

An adhesive resin composition comprising the following components (A), (B), and (C): (A) an epoxidized olefin resin, (B) a curing agent, and (C) a thermally decomposable foaming agent; an adhesive film made from the composition; an adhesive laminated film produced by laminating a support with the adhesive film; a laminate made by bonding an adherend to an adhesive layer formed by heating the adhesive film; and a method for peeling and recovering the adherend from the laminate by heating the laminate.

Description

 Specification

Adhesive resin composition and its use

 The present invention provides an adhesive resin composition comprising an epoxy resin containing an epoxy group, a curing agent, and a heat-decomposable foaming agent; an adhesive film obtained by forming the adhesive resin composition into a film; An adhesive laminated film obtained by laminating an adhesive film, a laminate obtained by bonding an adherend to an adhesive layer obtained by heating the adhesive film, and a laminate obtained by heating the laminate And a method for removing and recovering an adherend from a substrate. Background art

 Laminates obtained by bonding adherends through an adhesive layer of an adhesive film are widely used in automotive parts, home appliances, electrified products, office supplies, household goods, and the like. Japanese Patent Application Laid-Open No. Sho 64-142435 discloses that, after driving ethylene • <<, j3-unsaturated carboxylic acid copolymer and epoxy group-containing ethylene copolymer, extrusion molding is carried out. It is also disclosed that a laminated body strongly adhered to an adherend can be obtained via the obtained adhesive layer. -On the other hand, recently, in order to recycle (reuse) the adherend, a method of collecting the adherend from the laminate is required.

 However, the present inventors have studied and found that the adhesive layer in the laminate described in the above-mentioned Japanese Patent Application Laid-Open No. Sho 64-142435 has a strong adhesive force. It is difficult to easily peel off and collect the adherend without attaching it. Disclosure of the invention

 An object of the present invention is to provide an adhesive resin composition having excellent adhesion to an adherend and capable of easily peeling the adherend when the adherend is collected. The present invention

[1] An adhesive resin composition containing the following components (A), (B) and (C), (A): epoxy resin containing epoxy group

 (B): Curing agent

 (C): Thermal decomposition type blowing agent

[2] (A) component adhesive resin composition described in the following _(ai) and (a ₂₎ and an epoxy group-containing organic ethylene copolymers obtained by polymerizing (1),

( _ai ) ethylene (hereinafter sometimes referred to as ( _ai ) monomer)

(a ₂ ) a monomer represented by the following general formula (1), and

At least one monomer selected from the group consisting of monomers represented by the following general formula (2) (hereinafter sometimes referred to as (a ₂ ) monomer) ヽ X ヽ CH ₂ -CH : I (1)

 , 0

 (In the formula, R represents a hydrocarbon group having a double bond and having 2 to 18 carbon atoms, and a halogen atom may be bonded to the hydrocarbon group. X is a single bond or a carbonyl group. ) (2)

(In the formula, R ′ represents a hydrocarbon group having a double bond and having 2 to 18 carbon atoms, and a halogen atom may be bonded to the hydrocarbon group. Y is a carbonyl group [3] The component (A) is obtained by polymerizing a monomer copolymerizable with ethylene, which does not react with an epoxy group, the above-mentioned monomer) and the above-mentioned monomer (a ₂ ). The adhesive resin composition according to (1) or (2), which is a copolymer obtained by

[4] (B) component, the following (), (b ₂₎ and (b ₃₎ is that the ethylene-shed obtained by polymerizing a mono-unsaturated carboxylic acid copolymer [1] to [3] The adhesive resin composition according to any of the above,

It may be referred to as (b _x ) ethylene (hereinafter,) monomer. )

(b ₂ ), jS—unsaturated carboxylic acid and / or tri-unsaturated carboxylic anhydride (hereinafter sometimes referred to as (b ₂ ) monomer) (b ₃ ) vinyl ester and / or ct, jS—Unsaturated carboxylic acid ester (Hereinafter, it may be referred to as (b ₃ ) monomer.)

[5] The component (B) is used in an amount of 0.01 to 1 in terms of the structural unit derived from the monomer (b ₂ ) with respect to a total of 100 parts by weight of all the structural units constituting the component (B). 20 parts by weight, (b 3) the adhesive resin composition according to (4), which contains 25 to 70 parts by weight of a structural unit derived from a monomer,

[6] (A) component contains the _(ai) monomer and the (a ₂₎ epoxy group-containing ethylene copolymer is obtained, et al by polymerizing a monomer, (B) component the (B) a monomer, an ethylene-a,] 3-unsaturated carboxylic acid copolymer obtained by polymerizing the (b ₂ ) monomer and the (b ₃ ) monomer; The total content of the structural units is 30 to 75 parts by weight with respect to 100 parts by weight of the components (A) and (B) in any one of [1] to [5]. (7) The weight ratio of the component (A) to the component (B) is (A) / (B) = 90/100 to 40/60. The adhesive resin composition according to any one of the above (1) to (7), wherein the component (C) is an azodicarbonamide. Composition,

 [9] The adhesive property according to any one of [1] to [8], wherein the component (C) is 2 to 10 parts by weight based on 100 parts by weight of the total of the component (A) and the component (B). A resin composition, (10) an adhesive film obtained by forming the adhesive resin composition according to any of (1) to (9) into a film,

 [11] The adhesive film according to [10], which is obtained by press-molding a kneaded product obtained by kneading the adhesive resin composition.

 [12] The adhesive film according to [10], which is obtained by dissolving or dispersing the adhesive resin composition in a solvent, applying the composition on a flat surface, and drying.

 (13) an adhesive laminated film obtained by laminating the adhesive film according to any one of (10) to (12) on a supporting substrate,

(14) The support substrate according to (13), wherein the support substrate is at least one selected from a film made of polyolefin, a film made of release polyethylene terephthalate, a film made of cellulose triacetate, and release paper. Adhesive laminated film, obtained by heating the adhesive film according to any one of [15] [10] to [12] Laminate comprising an adhesive layer to be adhered and an adherend,

 [16] An adherend is laminated on the adhesive film layer side obtained by forming the adhesive resin composition of the adhesive laminated film according to [13] or [14] into a film. C) a laminate having an adhesive layer and an adherend, which can be obtained by heating and bonding at a temperature lower than the decomposition temperature of the components and then peeling off the supporting substrate,

 (17) An adherend is laminated on the adhesive film layer side obtained by forming the adhesive resin composition of the adhesive laminated film according to (13) or (14) into a film, and the supporting substrate is peeled off. After separation, a laminate having an adhesive layer and an adherend obtained by heating and bonding at a temperature lower than the decomposition temperature of the component (C),

 (18) An adherend is laminated on the adhesive film layer side obtained by forming the adhesive resin composition of the adhesive laminated film according to (13) or (14) into a film, and the supporting substrate is peeled off. After separating, an adhesive layer obtainable by laminating an adherend different from the adherend on the side from which the supporting base material has been peeled off and heating and bonding to a temperature lower than the decomposition temperature of the component (C) And a laminate having an adherend, and

 [19] The adherend is separated from the laminate by heating the laminate according to any one of [15] to [18] above the decomposition temperature of the component (C). To collect adherends

BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in detail.

 The component (A) in the present invention is an epoxy resin containing an epoxy group, and specifically, an olefin resin containing a carbon-carbon double bond such as Epofriend (registered trademark, manufactured by Daicel Chemical Industries, Ltd.). Examples include an olefin resin in which an epoxy group is generated by oxidation, and a resin obtained by polymerizing a monomer containing an epoxy group-containing carbon-carbon double bond.

Among the components (A), an olefin resin obtained by polymerizing a monomer containing an epoxy-containing carbon-carbon double bond is preferable. In particular, the ( _ai ) monomer and the (a ₂ ) monomer And an epoxy group-containing ethylene copolymer obtained by polymerizing , A1 copolymer. ) Is preferred.

 When the A1 copolymer is described in detail, R in the general formula (1) is a hydrocarbon group having a double bond, particularly a non-aromatic CC double bond and having 2 to 18 carbon atoms. R ′ in the formula (2) is a hydrocarbon group having a double bond, particularly a non-aromatic CC double bond and having 2 to 18 carbon atoms. In any hydrocarbon group, hydrogen on the hydrocarbon group The atoms may be replaced by halogen atoms.

 Specific examples of R and R 'include hydrocarbon groups represented by the following formulas (3) to (8).

H C: Two CH

 \ (3)

—X in general formula (1) is a simple bond between R and the oxygen atom in general formula (1). A bond or a carbonyl group.

Specific examples of the (a ₂₎ a monomer, § Li glycidyl ether, 2-Mechiruari Legris Siji Honoré ether, styrene - p - unsaturated Gurishijinore ethers such glycidyl ether; glycidyl § chestnut rate, glycidyl methacrylate, itaconic Thang And unsaturated dalicidyl esters such as ricidyl esters.

The content of the structural unit derived from the (a ₂ ) monomer in the A1 copolymer is usually in the range of 100 parts by weight of all the structural units constituting the epoxy group-containing ethylene copolymer. It is about 1 to 30 parts by weight. (A ₂ ) When the content of the structural unit derived from the monomer is 1 part by weight or more, the mechanical strength of the obtained adhesive film tends to be improved, so that it is preferably 30 parts by weight or less. It is preferable because the storage stability as an epoxy group-containing ethylene copolymer tends to be excellent.

The A 1 copolymer, not to react with an epoxy group, an ethylene copolymerized with available-monomer (hereinafter sometimes referred to as (a ₃₎ monomer.), I.e., () Single A monomer which is different from the monomer (a ₂ ) and is copolymerizable with ethylene is polymerized together with the monomer ( _ai ) and the monomer (a ₂ ). You may. Incidentally, (a ₃₎ monomer is a carboxylic acid group or a hydroxyl group, it does not contain functional groups capable of reacting with an epoxy group.

(A ₃₎ Specific examples of the monomer, methyl acrylate, Echiru acrylate, § acrylic acid n- propyl, isopropyl acrylate, n- butyl acrylate, § click acrylic acid t one heptyl, Isopuchiru acrylic acid, Methyl methacrylate, methyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate and isobutyl methacrylate having an alkyl group having about 3 to 8 carbon atoms <¾, β-unsaturated carboxylic acid alkyl ester; vinyl acetate, vinyl butyrate, vinyl propionate, vinyl piperate, vinyl laurate, vinyl isononanoate, versatic acid vinyl, etc. 3 to 20 carbon atoms such as propylene, 1-butene and isobutene Every time one Orefin; butadiene, isoprene, Jen compounds such as cyclopenta diene, vinyl chloride, styrene, acrylonitrile, Metaku Lilo two Torinore, acrylamide, and Bulle compounds such Metatariruami de ani I can do it.

The (a ₃₎ a monomer, among others, propylene, acetic Bulle, acrylic acid methylation, Atariru acid Echiru, Atariru acid n- butyl, methyl Metatariru acid Ru preferred der.

The content of the structural unit derived from the monomer (a ₃ ) in the A1 copolymer is usually calculated based on 100 parts by weight of all the structural units constituting the epoxy group-containing ethylene copolymer. It is about 0 to 70 parts by weight, particularly preferably about 25 to 60 parts by weight. (A ₃₎ to contain a structural unit derived from a monomer, and tends to be easily handled at the time of kneading the adhesive resin composition, the A 1 copolymer tends to easily dissolved in an organic solvent The amount is preferably 70 parts by weight or less, because the A1 copolymer tends to be easily produced by a high-pressure radical method or the like.

A 1 copolymers, block copolymers, graph preparative copolymer, a random copolymer may be any of alternating copolymer, for example, propylene - ethylene block copolymer (a ₂₎ Single A copolymer obtained by grafting an α,] 3-unsaturated carboxylic acid ester onto an ethylene-epoxy group-containing monomer copolymer Polymers (Japanese Patent No. 26020048) and the like.

 As a method for producing the A1 copolymer, for example, a monomer as a raw material other than ethylene is mixed with ethylene and a radical generator in the presence of ethylene and a radical generator at about 500 to 400 atm. A method of copolymerizing at about 0 ° C in the presence or absence of a suitable solvent or chain transfer agent; mixing a monomer that is a raw material other than ethylene with polyethylene together with a radical generator, And a method of melt graft copolymerization.

The A1 copolymer is commercially available, and such a commercially available product can also be used. Examples of such commercial products include “Bondfast (registered trademark)” series such as “Bondfast CG501”, “Bondfast E”, and “Bondfast 20B” (Sumitomo Chemical Ethylene copolymers and terpolymers with glycidyl methacrylate manufactured by Kogyo Co., Ltd .; Sepolsion G series (manufactured by Sumitomo Seika Co., Ltd.); be able to. The component (B) used in the present invention is a curing agent for epoxy, for example, amines such as aliphatic polyamines and aromatic polyamines; and polyamide polyamines obtained by deammonifying polycarboxylic acids and polyamines. Amides such as polyamides obtained by polymerizing amino acids; polymers containing carboxylic acid groups and acid anhydride groups; phenol novolaks; dicyandiamid, polysulfide, polymercaptan, dihydrazide, guanidine, imidazole, etc. Latent or hardening agent; heat or photo-ionizing polymerization initiator. As the component (B), two or more hardeners may be used.

Among the curing agents, a polymer containing a carboxylic acid group and an acid anhydride group is preferable, and in particular, a () monomer, a (b ₂ ) monomer, and a (b ₃ ) monomer are polymerized. The ethylene / _α , -unsaturated carboxylic acid copolymer (hereinafter sometimes referred to as B 1 copolymer) obtained by the above method is preferred.

 Further, the (1) copolymer will be described in detail.

The (b ₂ ) monomer in the B 1 copolymer; the 3-unsaturated carboxylic acid includes, for example, acrylic acid, methacrylic acid, crotonic acid, monoalkyl fumarate, monoalkyl malate and the like. Monocarboxylic acids; dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and 3,6-endomethylene-1,2,3,6-tetrahydrosis-phthalic acid. Examples of (b ₂ ) monomer,] -unsaturated carboxylic acid anhydride include the intramolecular or intermolecular anhydride of the a, j3-unsaturated carboxylic acid.

As the (b ₂ ) monomer, acrylic acid, methacrylic acid, and maleic anhydride are particularly preferable.

The content of the structural unit derived from the (b ₂ ) monomer in the B1 copolymer is usually 0.01 parts by weight based on 100 parts by weight of all the structural units constituting the B1 copolymer. About 20 parts by weight, preferably about 0.1 to 15 parts by weight. (B ₂ ) When the content of the structural unit derived from the monomer is at least 0.01 part by weight, the mechanical strength of the obtained adhesive film tends to be improved. Is preferred because it tends to have excellent storage stability as a B1 copolymer. No.

Examples of the unsaturated carboxylic acid ester of the (b ₃ ) monomer in the Bl copolymer include an α, β-unsaturated carboxylic acid alkyl ester having about 3 to 8 carbon atoms. Methyl acrylate, ethyl acrylate, η-propyl acrylate, isopropyl acrylate, η-butyl acrylate, t_butyl acrylate, isoptyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, Examples include isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and isobutyl methacrylate.

The vinyl ester of the (b ₃ ) monomer in the B1 copolymer includes a vinyl carboxylate having about 1 to 20 carbon atoms. Specifically, it includes vinyl acetate, vinyl butyrate, and vinyl propionate. Binore, vinyl-piperate, vinylinole laurate, biel isononanoate, vinyl versatate and the like.

 As the (b g) monomer, among them, vinyl acetate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are preferred.

In the B1 copolymer, the content of the structural unit derived from the monomer (b ₃ ) is usually 25 to 100 parts by weight of all the structural units constituting the B1 copolymer. To 70 parts by weight, preferably about 25 to 65 parts by weight. (B ₃ ) When the content of the structural unit derived from the monomer is 25 parts by weight or more, it is preferable because handling when kneading the adhesive resin composition of the present invention tends to be easy, Further, it is preferable because the B 1 copolymer tends to be easily dissolved in an organic solvent. The content of 70 parts by weight or less is preferable because the B1 copolymer tends to be easily produced by a high-pressure radical method or the like.

The adhesive resin composition of the present invention contains an A1 copolymer as the component (A), a B1 copolymer as the component (B), and the component (A) and the component (B). It is preferable that the total content of structural units derived from ethylene ( _{& 1} ) monomer () monomer is 30 to 75 parts by weight based on 100 parts by weight in total. .

As a method for producing the B1 copolymer, for example, a monomer as a raw material other than ethylene is mixed with ethylene and a radical generator in the presence of about 500 to 400 atm, At about 0 ° C, in the presence or absence of a suitable solvent or chain transfer agent. Method of mixing: a method of mixing a monomer which is a raw material other than ethylene with polyethylene together with a radical generator, and subjecting the mixture to melt graft copolymerization in an extruder.

 The B1 copolymer is commercially available, and such a commercially available product can also be used. Examples of the marketed products include “Bondane (registered trademark)” series (manufactured by Sumika AtoFina), “Let's Pearl ET” series (manufactured by Nippon Polyolefin Co., Ltd.), and “PRI MACOR” series (Dowow). Chemica 1).

 The weight ratio of the component (A) and the component (B) in the adhesive resin composition of the present invention is usually (A) / (B) = about 99/1 to 40/60. Within this range, the kneadability with the component (C) tends to be excellent, and the film tends to be easily formed.

 The melt flow rate (hereinafter referred to as MFR) when component (A) and component (B) are mixed is 5 to 400 g / l 0 at 190 ° C and 2.16 kg load. Minutes. As the component (C) in the adhesive resin composition of the present invention, for example, a foaming agent that decomposes when heated is mentioned, and specific examples thereof include an inorganic foaming agent and an organic foaming agent.

 Examples of the inorganic foaming agents include carbonate compounds such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, and ammonium nitrite; phosphate compounds such as polyphosphate amide, ammonium polyphosphate, and melamine phosphate. Carbonized materials such as starch, cellulose, saccharides and dipentaerythritol; light metals such as magnesium powder and aluminum powder; hydrides such as sodium borohydride and sodium hydride; and azides such as sodium azide.

Examples of the organic foaming agent include azo compounds such as azodicarbonamide and azobisisobutyl mouth-tolyl, dinitrosopentamethylenetetramine, nitroso compounds such as N, N'-dinitroso N, N'-dimethyl terephthalamide, p — Toluenesulfonylhydrazide, p, p '—Hydroxyzide compounds such as oxybis (benzenesulfonylhydrazide) and hydrazolcarbonamide, p-Toluenesulfonylazide Acetone-p-sulfonylhydrazone, melamine, urea, dicyanamide and the like.

 As the blowing agent, two or more types of blowing agents may be used. Further, among the foaming agents, organic foaming agents are preferable, and azodicarbonamide is particularly preferable.

 The content of the component (C) in the adhesive resin composition of the present invention is usually about 2 to 10 parts by weight based on 100 parts by weight of the total of the components (A) and (B). When the total amount of the component (C) is 2 parts by weight or more, the adherend tends to be easily separated and recovered from the obtained laminate. When the component (C) is 10 parts by weight or less, Adhesive strength tends to be stable. When the adhesive resin composition has a high adhesive strength to the adherend, the adherend can be easily separated from the laminate obtained by relatively increasing the content of the component (C). Can be. The adhesive resin composition of the present invention contains, for example, the components (A), (B) and (C) obtained as described above.

 The adhesive resin composition of the present invention includes an inorganic filler, a pigment, an antioxidant, a processing stabilizer, a weathering agent, a heat stabilizer, a light stabilizer, a nucleating agent, a lubricant, as long as the effects of the present invention are not impaired. Additives such as a release agent, a flame retardant, and an antistatic agent may be contained.

As a method for producing the adhesive resin composition, for example, a method in which the components (A), (B) and (C) and, if necessary, further additives are kneaded with a kneading machine such as Labo Plastomill to obtain a kneaded product. A method in which the kneaded material is further extruded by pressing, T-die processing with a single-screw or twin-screw extruder to obtain a film-like adhesive resin composition; (A), (B) and (C) ) A method for obtaining a liquid adhesive resin composition by dissolving or dispersing the components and, if necessary, further additives in an organic solvent; the emulsion-like component (A), the emulsion-like component (B) and the (C) Examples of the method include a method in which components and, if necessary, additives are further mixed to obtain an emulsion-like adhesive resin composition dispersed in water. The adhesive resin composition thus obtained can be used as it is as an adhesive, but the adhesive resin composition of the present invention is formed into a film to form an adhesive film. (Hereinafter sometimes referred to as the present adhesive film). The present adhesive film is formed, for example, by a method of press-molding a kneaded product obtained by kneading the adhesive resin composition of the present invention, dissolving or dispersing the adhesive resin composition of the present invention in a solvent, and coating the flat surface on a plane It can be easily obtained by a drying method.

 The thickness of the present adhesive film is usually about 3 μηι or more, preferably about 3 to 200 μm, and particularly preferably about 10 to 150 μm.

 The adhesive laminated film obtained by laminating the adhesive film on a supporting substrate (hereinafter sometimes referred to as the present adhesive laminated film) is easy to handle because the surface of the supporting substrate does not adhere. This is a preferred embodiment in terms of the point.

The present adhesive laminated film is, for example, a method of laminating the adhesive resin composition of the present invention obtained as a kneaded product and a supporting substrate by co-extrusion molding; A method of laminating the adhesive resin composition of the present invention in the form of a solution or an emulsion on a supporting base material, for example, a reverse roll coater, a gravure coater ¹ to a microno coater, a kiss coater, a Mayno coater, or air. It can be manufactured by a method such as coating with a lono-recorder such as a knife coater, a blade coater, etc., followed by drying with a heated air-open, a vacuum dryer or the like.

 Here, examples of the supporting substrate include films made of polyolefin such as polyethylene, polypropylene, and 4-methyl-1-pentene copolymer; release paper; films made of release polyethylene terephthalate; films made of cellulose triacetate, and the like. Is mentioned. Here, in the film made of release paper and release polyethylene terephthalate, these release treated surfaces are usually in contact with the present adhesive film layer in order to peel off the supporting substrate.

The temperature at the time of producing the present adhesive film or the present adhesive laminated film, such as extrusion molding, co-extrusion molding under pressure; kneading; drying, etc., is usually about the temperature required for performing these operations. And a temperature at which the component (C) in the adhesive resin composition of the present invention hardly foams, that is, a temperature not higher than the decomposition temperature of the component (C). About 20 ° C. The laminate in the present invention is a laminate comprising an adhesive layer obtained by heating the present adhesive film (hereinafter, may be referred to as the present adhesive layer) and an adherend. When the present adhesive laminated film is used, the supporting substrate is usually peeled off and removed. As a specific method for producing a laminate, for example, a method in which an adherend is laminated on the main adhesive film layer side of the main adhesive laminate film, bonded by heating, and then the supporting substrate is separated; A method of laminating an adherend on the main adhesive film layer side of the main adhesive laminate film, peeling off the supporting substrate, and heating; laminating the adherend on the main adhesive film side of the main adhesive laminate film; After the support base material is peeled off, a method in which an adherend different from the adherend is laminated on the surface from which the support base material is peeled off, and heating is performed.

 The heating temperature at the time of bonding varies depending on the type of the component (C) to be used, but it is lower than the decomposition temperature of the component (C), specifically, about 80 to 150 ° C. While confirming the state of adhesion by heating, the time can be appropriately determined within a range in which the decomposition of the component (C) does not substantially occur, but when performed at a relatively high temperature, the time is relatively short. In the case of performing at a low temperature, it is generally performed for a long time. In addition, the gel time at the set temperature of the adhesive resin composition of the present invention and the time required for foaming of the component (C) are confirmed in advance, and as a result, the time during which gelation occurs and foaming does not occur is determined. It can be determined as appropriate. Generally, it is appropriately selected and set at a temperature lower by about 5 to 20 ° C than the foaming temperature of the component (C) for about 5 to 60 minutes. During heating, a pressure of about 1 to 6 MPa may be applied by a press machine.

Here, the material constituting the adherend is a material that can adhere to the present adhesive layer. Specifically, for example, cellulosic polymer materials, metals such as gold, silver, copper, iron, tin, lead, and silicon; inorganic substances such as glass and ceramics; melamine resins, acrylic urethane resins, Examples include urethane-based resins, (meth) acryl-based resins, styrene-acrylonitrile-based copolymers, polycarbonate-based resins, phenolic resins, alkyd resins, epoxy resins, and polymer materials such as silicone resins. As the material of the adherend, two or more different materials may be mixed and compounded. Further, when the laminate is formed by bonding two different adherends via the present adhesive layer, the materials forming the two adherends are the same type of material but different types of materials. Either may be used. In addition, if the adherend has a heat resistance temperature higher than the heating temperature at the time of peeling and collecting the adherend, the interface between the adherend and the adhesive layer tends to peel off. preferable.

 The laminate thus obtained is required to peel and collect the adherend, such as refrigerators, washing machines, air conditioners, microwave ovens, vacuum cleaners, televisions, batteries, and other home appliances; personal computers, printers Office supplies such as copiers, fixed telephones, and mobile phones; automobiles such as bumpers and battery containers; furniture and housing structures; and other daily necessities; liquid crystal panels, semiconductors, printed wiring boards, integrated circuits, secondary battery containers, etc. It can be used for electronics products. In addition, the adhesive laminated film of the present invention can be used as a process release paper (primary adhesive protective paper) at the time of manufacturing, using an electronic product such as a semiconductor as an adherend.

 By heating the laminate of the present invention, the adherend can be easily peeled and recovered from the laminate, and can be recycled (reused). For example, when the present adhesive laminated film is used as a process release paper, the laminate is an intermediate product consisting of a process release paper (an adhesive layer obtained by heating the present adhesive film) and a product (adherend). When the process release paper is no longer needed, the product is easily released and collected by heating.

Specific methods for removing and recovering the adherend include, for example, placing the laminate in an oven, a hot water tank, etc. (C) is foamed by heating at about 120 to 240 ° C, and the adherend is peeled off and collected; flame, infrared rays, steam, ultrasonic waves, electromagnetic waves, etc. are applied to the laminate. Irradiation and foaming of (C) to peel and recover adherends: A method of placing a laminate on a heating body such as an iron plate, foaming (C) and peeling and recovering adherends, etc. Can be In any case, the temperature and time sufficient for the component (C) to foam from the present adhesive layer can be determined by appropriately combining them. For example, (C) the foaming temperature of the component to about + 20 ° C. and about 5 to 60 minutes can be mentioned. The adherend recovered in this way can be easily peeled off from the laminate, and the adherent hardly has the substance derived from the present adhesive layer or has the substance derived from the present adhesive layer attached thereto. Even if it is worn, it can be easily separated from the adherend, and the adherend can be recycled (reused) or easily obtained as a product. The recovered adherend such as metal or plastic may be melted, separately molded, and reused. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Parts in the examples are by weight unless otherwise specified.

 The following (A), (B) and (C) components were used. The MFR (melt flow rate) is a value measured under the conditions of 190 ° C and a load of 2160 g according to JIS K 72010.

 (A) Ingredient

 A: Sumitomo Chemical Industries, Ltd. “Bondfast CG 500 1”

 Ethylene-methyl acrylate-daricidyl methacrylate copolymer, content of structural unit derived from glycidyl methacrylate 18% by weight MF R = 360 g / 10 minutes

 (B) Ingredient

 B: (with) Sumika AtoFina "Bondane HX821 0J,

 Ethylene-ethyl acrylate-maleic anhydride copolymer,

 6% by weight of structural units derived from ethyl acrylate, 3% by weight of structural units derived from maleic anhydride,

 MFR = 200 g / l Omin

 (C) Ingredient

 C: Sankyo Kasei Co., Ltd. “Cell Microphone C—1 2 1”,

 Azodicarbonamide, decomposition temperature 205 ° (average particle size 10-14 μm (Examples 1-3 and Comparative Example 1)

 (1): Production example of adhesive resin composition

A, B, and C were added to a small patch-type kneader “Lab Plasminore” (manufactured by Toyo Seiki Seisakusho Co., Ltd., 50C150, mixer: R100H) at the weight ratios shown in Table 1. Preset for 7 minutes at 10 rpm under the condition of a barrel set temperature of 100 ° C. After the preliminary kneading, the final kneading was performed at 50 rpm for 5 minutes to obtain an adhesive resin composition.

(2): Production example of adhesive laminated film

 After hot-pressing the adhesive resin composition obtained in (1) under the preforming conditions described below, a SUS plate and a fluorine resin sheet were added to the hot plate of the hot press preheated to 100 ° C. Are sequentially laminated, a polyethylene terephthalate mold and the obtained preform are placed on the fluororesin sheet, a fluororesin sheet and a SUS (stainless) plate are further placed, and heat is applied according to the film forming conditions described below. Pressing was performed to obtain an adhesive film.

Subsequently, a laminator “VA-700” (manufactured by Taisei Laminator) was superimposed on the release surface of a polyethylene terephthalate film “Emblet sc” (manufactured by Unitichika), which was obtained by releasing the adhesive resin composition in the form of a film. Using the roll temperature: 80. C, mouth Lumpur rate: 0. 5 m / min, mouth Lumpur ^{pressure: 4. 9 X 1 0 4 P} a (0. 5 kgf / cm 2, gauge reading) by thermal lamination under the conditions of, (a support Base material: release polyethylene terephthalate film) / (adhesive film layer) adhesive laminate finolem was obtained.

 <Preliminary molding conditions>

 1 20 mmX 1 20 mm X 1 mm thick

Hot plate set temperature 100 ° C, preheating 10 minutes (3 times dumping)

Heating pressure: 50 kg / cm ² XI min → 100 kg / cm ² XI min

→ 150 kg / cm ² , cooling 100 kg / cm ² X 2 minutes, molding conditions>

 Formwork 1 50 mmX 75 mmX 0.1 mm thick,

Hot plate set temperature 100 ° C, preheating 10 minutes (3 times dumping)

Pressurizing pressure: 50 kg / cm ² XI min → 100 kg / cm ² XI min

→ 1 50 kg / cm ² , cooling l OO kg / cm ² X 2 minutes

(3): Production example of laminate

After cutting the adhesive laminated film obtained in (2) to a width of 25 mm, An s US (stainless steel) or slide glass was laminated as an adherend on the film. That is, the layers were laminated from the bottom in the order of (supporting substrate) / (adhesive film layer) / (adherend). Next, after the supporting substrate was peeled by hand, a polyethylene terephthalate film (PET film) not subjected to the following release treatment was laminated as a substrate, and the obtained (substrate) / (adhesiveness) was obtained. The film layer) / (adherend) was heated from above and below using a heat filter tester (“Heat Seal Tester TP-701-B” manufactured by Tester Sangyo Co., Ltd.) at 150 ° C, 9.8 X 10 ⁴ Heat sealing was performed at a pressure of Pa (gauge pressure: 1 kgf / cm ² ) for 30 minutes to obtain a laminate of the present invention. The adherends used were as follows, and the components (A) to (C) contained in the adhesive resin composition used and the adherends are shown in Table 1.

Substrate.

 SUS: SUS 304 flat plate 1 60 mmX 65 mmX 0.8 mm thick Slide glass: MAT S UNAM I Co., Ltd. SI 126

 76 mmX 26 mmX 1 Omm thickness Surface polished

<Substrate>

 PET film: D I AF〇 I L T 600 E 50 -W07 50 μm thick

 Double coated film made of Mitsubishi Chemical polyester film

(4) Measurement of adhesive strength before heating

 After preparing the laminate obtained in (3) at a temperature of 23 ° C and a relative humidity of 50% for 1 hour, a test of 1 Omm width x 10 Omm length (adhesion length 25 mm) A piece was cut out and subjected to a peeling test under the conditions of a temperature of 23 ° C and a relative humidity of 50% at a peeling rate of 10 Omm / sec and a peeling angle of 180 °. (5) Heat peelability test

 The laminate prepared in (3) was placed on a hot plate heated to 240 ° C. with the adherend facing down, heated for 5 minutes, and the state was observed. The results are shown in Table 1.

 The judgment was based on the following criteria. '

〇: The adherend was immediately separated. X: The adherend could not be easily separated. Table 1

 * 1: Number of copies of C for 100 copies of A and B

 A: Interface peeling between adherend and adhesive layer

 A: Interface peeling between adherend and adhesive layer, and

 Mixing of cohesive peeling of adhesive layer The adhesive film obtained by molding the adhesive resin composition of the present invention has a dry film form that is easy to handle such as storage, transportation, and bonding workability before bonding. It is possible to form an adhesive layer having excellent adhesive strength by having and bonding by heating. Then, simply by heating, the adhesive strength is easily reduced and the adherend is easily peeled off and collected, and the collected adherend is almost free of adhesive from the adhesive film. Even if it adheres, the adherend can be easily peeled off, and the adherend can be recycled (reused).

Utilizing such excellent properties, the laminate of the present invention can be used, for example, in semiconductor encapsulants, electronic component encapsulation materials such as solar cells and EL (electroluminescence) lamps, and between integrated circuit Z substrates. Die bonding sheet It can be used for solder resist of printed wiring boards, decorative films for automobile parts, etc., and plasma displays. It can also be used as a process release paper during semiconductor manufacturing, etc.

Claims

Scope of claim

1. An adhesive resin composition containing the following components (A), (B) and (C).

(A): epoxy resin containing epoxy group

 (B): Curing agent

 (C): Thermal decomposition type blowing agent

2. (A) component and below _(ai) (a ₂₎ an adhesive resin composition in the range described in the first paragraph according to an epoxy group-containing ethylene copolymer obtained by polymerization.

(a _x ) ethylene

(a ₂ ) a monomer represented by the following general formula (1), and

 At least one monomer selected from the group consisting of monomers represented by the following general formula (2)

X ヽ CH ₂ -CH (1)

(Wherein, R represents a hydrocarbon group having a double bond and having 2 to 18 carbon atoms, and a halogen atom may be bonded to the hydrocarbon group. X is a single bond or a carbonyl group. Represents.)

 (In the formula, R ′ represents a hydrocarbon group having a double bond and having 2 to 18 carbon atoms, and a halogen atom may be bonded to the hydrocarbon group. Y is a carbonyl group Represents.)

3. (A) component, not to react with an epoxy group, an ethylene copolymerized with available-monomer, wherein _(ai) and the co-obtained by polymerizing a monomer (a ₂₎ 3. The adhesive resin composition according to claim 1, which is a polymer.

4. The component according to claims 1 to 3, wherein the component (B) is an ethylene 'α, —unsaturated carboxylic acid copolymer obtained by polymerizing the following (), (b ₂ ) and (b ₃ ). The adhesive resin composition according to any one of the above.

(b ₁ ) ethylene

(b ₂ ) a, j3-unsaturated carboxylic acid and / or a, j3-unsaturated carboxylic acid Acid anhydride

(b ₃ ) vinyl esters and / or 0-unsaturated carboxylic esters

5. The component (B) is used in an amount of 0.01 to 20 parts by weight of the structural unit derived from (b ₂ ), based on a total of 100 parts by weight of all the structural units constituting the component (B); _3. The adhesive resin composition according to claim 4, which contains 25 to 70 parts by weight of a structural unit derived from ₃ ).

6. containing component (A) is the () and the (a ₂₎ with an epoxy group obtained by polymerizing containing ethylene copolymer, Oyo component (B) above), the (b ₂₎エ チ レ ン Contains an ethylene-a, jS-unsaturated carboxylic acid copolymer obtained by polymerizing the above (b ₃ ), and the total content of the structural units derived from ethylene is as follows. The adhesive resin composition according to any one of claims 1 to 5, wherein the amount is 30 to 75 parts by weight based on 100 parts by weight of the component (B) in total.

 7. The adhesive according to any one of claims 1 to 6, wherein the weight ratio of the component (A) to the component (B) is (A) no (B) = 90/10 to 40/60. Resin composition.

8. The adhesive resin composition according to any one of claims 1 to 7, wherein the component (C) is azodicarbonamide.

 9. The adhesive resin according to any one of claims 1 to 8, wherein the component (C) is 2 to 10 parts by weight based on a total of 100 parts by weight of the components (A) and (B). Composition

10. An adhesive film obtained by forming the adhesive resin composition according to any one of claims 1 to 9 into a film.

 11. The adhesive film according to claim 10, which is obtained by press-molding a kneaded product obtained by kneading the adhesive resin composition.

 12. The adhesive film according to claim 10, wherein the adhesive resin composition is dissolved or dispersed in a solvent, applied on a flat surface, and dried.

 1 3. An adhesive laminated film obtained by laminating the adhesive film according to any one of claims 10 to 12 on a supporting substrate.

14. The supporting base material is a film composed of polyolefin, a film composed of release polyethylene terephthalate, a film composed of cellulose triacetate, and release paper. 14. The adhesive laminated finolem according to claim 13, which is at least one type selected from the group consisting of:

 15. A laminate comprising an adhesive layer obtained by heating the adhesive film according to any one of claims 10 to 12, and an adherend.

 16. An adherend is laminated on the adhesive film layer side obtained by film-forming the adhesive resin composition of the adhesive laminated film according to claim 13 or 14, and the laminate is referred to as ( C) A laminate having an adhesive layer and an adherend that can be obtained by heating and bonding at a temperature lower than the decomposition temperature of the components and then peeling off the supporting substrate.

 17. An adherend is laminated on the adhesive film layer side obtained by forming the adhesive resin composition of the adhesive laminated film according to claim 13 or 14 into a film, and the supporting substrate is peeled off Thereafter, a laminate having an adhesive layer and an adherend obtainable by heating and bonding at a temperature lower than the decomposition temperature of the component (C).

 18. An adherend is laminated on the adhesive film layer side obtained by forming the adhesive resin composition of the adhesive laminated film according to claim 13 or 14 into a film, and the supporting substrate is peeled off Then, an adhesive layer obtained by laminating an adherend different from the adherend on the side from which the supporting base material has been peeled off, and heating the adhesive to a temperature lower than the decomposition temperature of the component (C) to form an adhesive layer A laminate having an adherend.

 19. The adherend is separated from the laminate by heating the laminate according to any one of claims 15 to 18 above the decomposition temperature of the component (C). How to recover the adherend.