TW200401019A - Adhesive resin composition and use thereof - Google Patents

Abstract

This invention provides 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

200401019 ⑴ 发明, Description of the invention [Technical field to which the invention belongs] The present invention relates to an adhesive resin composition composed of an epoxy-containing olefin resin, a hardener, and a thermal decomposition type foaming agent, and the adhesive resin composition An adhesive film formed from a thin film, an adhesive laminated film formed by laminating the adhesive film on a supporting substrate, a laminated body formed by adhering an adherend to an adhesive layer obtained by heating the adhesive film, A method for heating the laminated body to peel it from the laminated body and recover the adherend. [Previous technology] Laminated systems obtained by adhering adherends through an adhesive layer of an adhesive film are widely used in automotive parts, such as home appliances, electronics, office products, and daily necessities. Therefore, Japanese Unexamined Patent Publication No. 6 4-I 4 2 3 5 also discloses that an ethylene · α'Θ-unsaturated carboxylic acid copolymer and an epoxy-containing ethylene copolymer are dry-blended and then extruded through The obtained adhesive layer is compression-molded to obtain a laminated body strongly adhered to the adherend. On the other hand, recently, in order to recover (reuse) the adherend, there is a desire for a method of peeling off the laminated body and recovering the adherend. However, after review by the present inventor, it was found that the laminated body described in the aforementioned Japanese Patent Application Laid-Open No. 64-14234235 has no problem in attaching the laminated body to the adhesive layer because the adhesive layer has strong adhesive force, but it is difficult to be adhered. Body peeling recovery. [Summary of the Invention] -6- (2) 200401019 The object of the present invention is to provide an adhesive resin composition which is excellent in adhesion to an adherend and can easily peel the adherend when recovering the adherend. The present invention provides [1] an adhesive tree composition containing the following components (A), (B), and (C): (A): an epoxy-containing olefin resin, (B): a hardener (C ) •• Thermal decomposition type foaming agent. [2] The adhesive resin composition described in the item [1], wherein the component (A) is an epoxy group-containing ethylene-based copolymer obtained by polymerizing the following (ai) and (a2): (a!) Ethylene (Hereinafter also referred to as (ai) monomer), (a2) at least one monomer selected from the group consisting of a monomer represented by the following general formula (1) and a monomer represented by the following general formula (2) Called (a2) monomer), R. .0. /? H2 \ χ / \ cH2-CH \ | ⑴ ο (where r represents a hydrocarbon group having 2 to 18 carbon atoms having a double bond, and the hydrocarbon group may also be Combined with halogen atom, X shows single bond or carbonyl group), R | —0—CO-CH2-CH:

2 (3) 200401019 (wherein R1 represents a hydrocarbon group having 2 to 8 carbon atoms having a double bond and may be bonded to a halogen atom, and Y represents a carbonyl group). [3] The component (A) of the adhesive resin composition (A) described in the item [1] or [2] is polymerized by the (a!) Monomer and (as) monomer copolymerizable with ethylene without reacting with epoxy groups. The copolymer obtained, the adhesive resin described in any one of [4] [1] to [3], wherein the component (B) is ethylene · α of the following (bl), (b2), and (b3). 3-unsaturated carboxylic acid copolymer, (b) ethylene (hereinafter also referred to as (bl) monomer), (b2) a, yS-unsaturated carboxylic acid and / or a, unsaturated (also referred to as (hereinafter b2) a monomer), (b3) a vinyl ester and / or an α, fluorene-unsaturated carboxylic acid ester (which is a (b3) monomer), and the adhesive resin composition according to [5] [4], wherein: Divided into the total amount of all structural units constituting component (B), containing 0.01 to 20 structural units derived from (b2) monomers, and 25 to 70 parts by weight of structural units derived from (b3) monomers, [6] [ 1] The adhesive resin according to any one of [5], wherein the component (A) is an epoxy group-containing ethylene-based copolymer containing the above (ai) monomer and (a2), (B) (Bl) monomer, (b2) monomer and (b3) monomer above · Α '/ 3 -Unsaturated carboxylic acid-based copolymer, which is derived from the unit of manufacture, and its total content is based on (A) component and (B) component group, the hydrocarbon compound, the monomer, the upper compound, and The carboxylic anhydride is hereinafter referred to as (B) as 100 parts by weight, and the composition of the monomer is divided into the aforementioned polymerization to obtain the structure of ethylene W ™ f μ Zn g -8-(4) (4) 200401019 100 parts by weight, 30 to 75 parts by weight, the adhesive resin composition according to any one of [7] [1] to [6], wherein the weight ratio of the component (A) to the component (B) is ( A) / (B)

A = 90/10 to 40/60 'The adhesive resin composition described in any one of [8] [1] to [7]', wherein (C) the component is azobiscarboxamide, [9] The adhesive resin composition according to any one of [1] to [8], wherein the total amount of (A) component and (B) component is 100 parts by weight, and contains (C) component 2 to 1 〇Part by weight, [10] An adhesive film obtained by forming the adhesive resin composition described in any one of [1] to [9] into a thin film, described in [11] [1 〇] The adhesive film is obtained by pressure-molding the kneaded product obtained by kneading the adhesive resin composition. The adhesive film described in [1 2] [1 0] is a solution or dispersion of the adhesive resin composition. [1 3] —a kind of adhesive laminated film, which is laminated on a supporting substrate according to any one of the items [! 〇] to [1 2] after being applied on a flat surface after being dried in a solvent. The adhesive laminated film described in [1 4] [1 3], which is composed of an adhesive film, wherein the supporting substrate is at least one selected from the group consisting of a polyolefin film and a release polyethylene terephthalate [15] A laminated body, an adhesive layer obtained by heating the adhesive film according to any one of [10] to [I2], and a film composed of cellulose triacetate and a release paper. And the adherent, (5) (5) 200401019 [16] A laminated body with an adhesive layer and an adherend is a layer of the adherent volume to the adherence described in [1 3] or [1 4] The laminated layer film _ occupies the side of the adhesive layer formed by thinning the resin composition, and the laminated layer is heated and adhered below the decomposition temperature of the component (C), and the support substrate is peeled off, [17 ] A laminated body having an adhesive layer and an adherend, which is an adhesive formed by thinning an adhesive resin composition having an adhesive volume layer in the adhesive laminated film described in [1 3] or [1 4] On the side of the layer, after the support substrate is peeled off, it is obtained by heating and sticking below the decomposition temperature of the component (C). [18] A kind of laminated body having an adhesive layer and an adherend, which is to be adhered to the bulk layer. [13] or [14] The adhesive resin composition of the adhesive laminated film according to [14] is formed into a thin film On the adhesive layer side, after the support substrate is peeled off, an adherend different from the adherend is laminated on the release surface side of the support substrate, and the adhesive is heated and adhered below the decomposition temperature of the component (C), And [1 9] A method for recovering an adherend, characterized in that the laminate according to any one of π 5] or π 8] is heated above the decomposition temperature of the component (C), and the adherend is Method of peeling the laminated body. [Embodiment] Best Mode for Carrying Out the Invention Hereinafter, the present invention will be described in detail. The component (A) of the present invention is an epoxy-containing olefin resin, which can be specifically exemplified by Epoflend (registered trademark, Big Sher-10-(6) 200401019 (D aice) 1) Chemical Industry Co., Ltd. Co., Ltd.), etc., olefin resins that generate epoxy groups by oxidizing olefin resins containing carbon and carbon double bonds; resins made by polymerizing monomers containing carbon and carbon double bonds containing epoxy groups, etc. . The (A) component is preferably an olefin resin obtained by monopolymerization containing an epoxy-containing carbon · carbon bicarbonate, especially an epoxy-containing resin obtained by polymerizing the above (ai) monomer and (a2) monomer. A vinyl copolymer (hereinafter also referred to as an A! Copolymer) is more preferred. In a more detailed description, when the A 1 copolymer is in the general formula (1), R is a hydrocarbon group having a double bond, especially a non-aromatic CC double bond having 2 to 18 carbon atoms. In the general formula (2), R1 is a Bonds, especially non-aromatic CC double bonds, have a carbon number of 2 to 18, and any hydrocarbon group may have a hydrogen atom substituted on its hydrogen group by a halogen atom. R and 1 can be specifically exemplified by hydrocarbon groups and the like represented by the following formulae (3) to (8).

H2C

CH

(3)

H2C

(4) h2c

(5) h2c

CH2— (6) -11- (7) 200401019

⑺

H3C

(8) X in the general formula (1) represents a single bond or a carbonyl group in which the oxygen atom in the general formula (1) and R are directly bonded. (a2) Specific examples of the monomer include unsaturated glycidyl ethers such as allyl glycidyl ether '2-methylallyl glycidyl ether, styrene-p-glycidyl ether; glycidyl acrylate, glycidyl Unsaturated glycidyl esters such as methacrylate and glycidyl itaconic acid. The content of the structural unit derived from the (a2) monomer in the A! Copolymer is 100 parts by weight to the structural unit constituting the epoxy-based ethylene-based copolymer, and generally contains about 1 to 30 parts by weight. If the content of the structural unit derived from (a2) monomer is 1 part by weight or more, the mechanical strength of the obtained adhesive film is improved, and if it is 30 parts by weight or less, the epoxy group-containing ethylene-based copolymer is Preservation stability is superior and better. Monomer copolymerizable with ethylene without reacting with epoxy groups (hereinafter also referred to as (a3) monomer), that is, different from (ai) monomer and (a; 2) monomer The monomer copolymerizable with ethylene is polymerized together with (ai) monomer and (a2) monomer. In addition, the '(µ) monomer does not contain a functional group capable of reacting with an epoxy group such as a carboxylic acid group or a hydroxyl group. -12- (8) 200401019 (a3) monomers can be specifically exemplified as having methyl acryl, n-propyl acrylate 'isopropyl acrylate, second acrylic acid acrylate' isobutyl acrylate, ethyl methacrylate Vinegar, n-propyl methacrylate, n-butyl methacrylate, third butyl methacrylate, and methacrylic acid have about 3 to 8 alkyl a, / S-unsaturated carboxyethyl Vinegar, vinyl butyrate, vinyl propionate, ethylene terephthalate trimethyl laurate, vinyl isononanoate, vinyl esters of about 2 to 8 residual acids of ethylene sebacate; propylene, butylene, iso-3 20 to 20 olefins; butadiene, isoprene, cyclic compounds; ethylene chloride, styrene 'acrylonitrile, methacrylic acid, methacrylamide and other ethylene compounds. (as) Monomers are propylene, vinyl acetate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate. Al copolymers are derived from (a3) monomers. The structural unit of the copolymer contains about 0 to 70 parts by weight, especially about 25 to 60 parts of the structural unit derived from the (a3) monomer, which is easier to handle when kneading the adhesion, and The A! Copolymer is more preferred, and if the content is 70 parts by weight or less, the A! Copolymer can be easily produced by the base method and the like. The copolymer may be any of a block copolymer, a graft copolymer, and an alternating copolymer, for example, a copolymer obtained by grafting propylene-ethyl with (as) monomer (Japanese patent; ester, ethyl n-butyl acrylate) Acid alkyl esters such as esters, propylene esters, methacrylic propyl esters, isobutyl methacrylate, and the like; vinyl acetate, esters, and other diene acrylonitriles and acrylic acids, such as vinyl acetate, butene, and carbon; Methyl esters and propylene are preferred. The content is better than the constituent parts, and generally the parts are better. The resinous composition is dissolved in an organic solvent by a high-pressure free substance, a random copolymerized olefin block copolymer No. 2632980. 13- (9) (9) 200401019 Gazette), a copolymer obtained by grafting an ethylene-epoxy group-containing copolymer with ο:,-unsaturated carboxylic acid ester (Japanese Patent No. 2 6 0 0 2 4 8 (Gazette) ΛτΑ- TeraA! Copolymer production method 'for example,' in the presence of ethylene and a radical generator, the raw material monomer other than ethylene 'is about 5,000 to 4,000 air pressure' about 1 0 0 to 3 0 0 ° C, a method of copolymerization in the presence or absence of a suitable solvent or chain transfer agent; Mixing raw materials other than ethylene and the vinyl monomer with the radical generator, a method of melt graft copolymerization in an extruder temple square

Ai copolymer is commercially available, and the commercially available product can be used. The commercially available products are "Bond Fast (registered trademark)" (Sumitomo) such as "Bond Fast CG5001", "Bond Fast E", "Bond Fast 20B", etc. Ethylene Copolymer and Ethylene Terpolymer of Glycyl Methacrylate Refined (Stock) System, "Sepogeon G" System (Sumitomo Refined (Stock) Co., Ltd. "RA (LuxpearRA)" (made by olefin (financial)), etc. The component (B) used in the present invention is a hardener for epoxy resins, such as aliphatic polyamines, aromatic polyamines, and the like. Amines such as amines; polyamines such as polyamines obtained by the deamination reaction of polycarboxylic acids and polyamines; polyamines such as polyamines obtained by polymerization of amino acids; polymers containing carboxylic acid groups and anhydride groups; phenolic aldehydes Lacquer resin, dicyandiamide, polysulfide, polythiol, dihydrazine, guanidine, imidazole and other potential hardeners; thermal or photocationic polymerization initiators, etc., (B) can also be used in two types The above hardener. -14- (10) (10) 200401019 Among the hardeners, polymers containing carboxylic acid groups and acid anhydride groups are preferred, especially Ethylene • a, -unsaturated carboxylic acid copolymer (hereinafter also referred to as B 1 copolymer) obtained by polymerizing (b!) Monomer and (b 2) monomer with (b 3) monomer is more preferred. The B 1 copolymer will be described in further detail. The α, square-unsaturated carboxylic acid as the (b 2) monomer in the B 1 copolymer may be exemplified by acrylic acid, methacrylic acid, butenoic acid, and monoalkyl fumaric acid. Esters' monoalkyl maleates and other monocarboxylic acids; maleic acid, fumaric acid, itaconic acid, citraconic acid, 3,6-Uchidabashi-1,2,3,6-tetrahydro-cis -Dicarboxylic acids such as phthalic acid, etc. In addition, the α, non-unsaturated carboxylic acid of (b2) monomer may be exemplified by the above-mentioned a, A-unsaturated carboxylic acid anhydride in or between molecules. b2) Acrylic acid, methacrylic acid, and maleic anhydride are used as monomers in the monomers. The content of the structural unit derived from the (b2) monomer in the B! copolymer is 100 weight to the entire structural unit constituting the 3! copolymer. Parts, generally about 0.01 to 20 parts by weight, preferably about 0.1 to 15 parts by weight. If the content of the structural unit containing the monomer derived from (b2) is 0.01 parts by weight or more, the resulting adhesiveness film The mechanical strength is improved, and if it is less than 20 parts by weight, the storage stability of the B! Copolymer is superior and excellent. The unsaturated carboxylic acid ester of the (b3) monomer in the 6 ^ copolymer can be exemplified by the carbon number as Α, A-unsaturated carboxylic acid esters of about 3 to 8, specifically exemplified by methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, third butyl acrylate, isopropyl acrylate Butyl ester 'methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, methacrylic acid-15- (11) 200401019 isopropyl ester, n-butyl methacrylate, and methacrylic acid B. The vinyl ester of the (b3) monomer in the copolymer may be, for example, a vinyl carboxylate having a carbon number of 20, and specific examples are vinyl acetate, Tg, vinyl ethylene propionate, trimethyl vinyl acetate, Ethyl laurate, vinyl ester, vinyl sebacate, etc. Among the (bs) monomers, vinyl acetate, methyl acrylate, propyl ester, n-butyl acrylate, and methyl methacrylate are preferred. The structure derived from the (h) monomer in the B1 copolymer is 100 parts by weight of the entire structural unit containing the B1 copolymer, generally about | 70 parts by weight, and preferably about 25 to 65 parts by weight. When the content of the structural unit derived from (b3 is 25 parts by weight or more, it is easier to handle the resin composition of the present invention when it is kneaded, and it is preferred that MB is easily dissolved in an organic solvent. If the content is At a weight of 70%, it is preferable because B can be easily produced by a high-pressure radical method, etc. The adhesive resin composition of the present invention contains a 1 co-polymer; (A) component, and the B1 copolymer is (B) And the total amount of (a) and (B) components is 100 parts by weight, and the total amount of the structural units derived from (ai) monomer and monomer ethylene is preferably 30 to 75 weight. B 1 Copolymer Manufacturing Method 'for example' in the presence of ethylene and free agent, the raw material monomers other than ethylene, at the pressure of about 501, about 1000 to 300 ° C, in the absence of a suitable solvent or chain transfer agent The following copolymerization method; the raw material other than polyethylene and ethylene is about 1 to ene ester, the amount of ethyl isononanoate to structure I 25 to) the amount of the adhesive copolymer of the monomer is based on the copolymer polymer and (bl) Participants are generated on a base! 4 000 Presence or monomer is mixed with -16- (12) (12) 200401019 free radical generator , Melt graft copolymerization in an extruder, etc. The B 1 copolymer is commercially available and can be sold in this market. The commercially available products are, for example, "Bondyn (registered trademark)" system (Sumika Chemicals Co., Ltd.'s Atfuna system), "Rishizhu ET" system (Japanese Polyolefins Co., Ltd.'s system), "PRIMACOR Department (made by Dow Chemical) and so on. The weight ratio of the component (A) and the component (B) in the adhesive resin composition of the present invention is generally about (A) / (B) = 99/1 to 40/60. Within this range, it has excellent kneading properties with the (C) component, and it is easier to form a thin film. The melt flow rate (hereinafter referred to as MFR (Melt Flow Rate)) when the components (A) and (B) are mixed is preferably 5 to 400 g / 10 minutes under conditions of 190 ° C and a load of 2.16 kg. . The component (C) in the adhesive resin composition of the present invention may be, for example, a foaming agent which is decomposed by heating, and specific examples thereof include an inorganic foaming agent and an organic foaming agent. Examples of the inorganic foaming agent include carbonate compounds such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, and amine nitrite; phosphate compounds such as ammonium polyphosphate, ammonium polyphosphate, and melamine diphosphate; source powder, Carbon compound materials such as cellulose, sugars and dipentaerythritol; light metals such as magnesium powder and aluminum powder; hydrides such as sodium borohydride and sodium hydride; and azide compounds such as sodium azide. The organic blowing agent may be exemplified by azo compounds such as azobiscarboxamide, azobisisobutyronitrile, dinitrosopentamethylenetetramine, N, N1-dinitroso · N, N, _monomethyl Nitroso compounds such as p-toluene methylamine, p-toluenesulfonic acid, p-p-tolyl bis (benzenesulfonylhydrazine), hydrazine compounds such as hydrazinocarboxamide, p-toluenesulfonamide, acetone -P-sulfuronium sulfonate, melamine, urine-17- (13) (13) 200401019, dicyanamide, etc. As the foaming agent, two or more foaming agents may be used. Among the blowing agents, organic blowing agents are preferred, and azobiscarboxamide is more preferred. In the adhesive resin composition of the present invention, the content of the component (C) is 100 parts by weight with respect to the total of the components (A) and (B), and is generally about 2 to 10 parts by weight. If the total amount of the component (C) is 2 parts by weight or more, it is easy to peel off the laminated body and recover the adherend. When the component (C) is 10 parts by weight or less, the adhesive force tends to be stable. In addition, when the adhesive force of the adhesive resin composition to the adherend is high, by containing a larger amount of the component (C), the adherend can be easily peeled from the obtained laminated body. The adhesive resin composition of the present invention contains, for example, the components 2 (A), (B), and (C) obtained as described above. The adhesive resin composition of the present invention may also contain inorganic materials, pigments, antioxidants, processing stabilizers, weathering agents, heat stabilizers, light stabilizers, nuclear agents, and lubricants, as long as they do not impair the effects of the present invention. , Release agent 'flame retardant, antistatic agent and other additives. The manufacturing method of the adhesive resin composition is, for example, a method of kneading the components (a), (B), and (C) components and additives as needed by a kneading machine such as a Laboplast mill to obtain a kneaded material; A method of further extruding the kneaded material, and extruding it with a T-die by a uniaxial or biaxial extruder to obtain a film-like adhesive resin composition; (A), (B), and ( C) Ingredients and other additives as needed 丨 Method for dissolving or dispersing in an organic solvent to obtain a liquid adhesive resin composition; emulsifying the (A) component and the emulsifying (B) component-18- (14) (14) 200401019 and (C) component 'and a method of mixing and dispersing other additives in water as necessary to obtain an emulsified adhesive resin composition, and the like. The adhesive resin composition thus obtained can be used directly as an adhesive, or the adhesive resin composition of the present invention can be converted into an adhesive film (hereinafter also referred to as the present adhesive film) by using a thin film. The adhesive film is, for example, a method of pressure-molding a kneaded material obtained by kneading the adhesive resin composition of the present invention; the adhesive resin composition of the present invention is dissolved or dispersed in a solvent, coated on a flat surface, and subjected to It can be obtained by drying. The thickness of the present adhesive film is generally about 3 m or more, preferably about 3 to 200 # m, and particularly preferably 10 to 150 from m. The adhesive laminated film (hereinafter also referred to as the adhesive laminated film) obtained by laminating the adhesive film on the substrate is easy to use because it is not adhered to the surface of the supporting substrate, which is a better style. The manufacturing method of the adhesive laminated film is, for example, a method in which the obtained adhesive resin composition is used as a kneaded material and is laminated by co-extrusion with a supporting substrate; the supporting substrate is laminated and adhered by extrusion molding. Method for applying a thin film; the solution-type or emulsion-type adhesive resin composition of the present invention is, for example, a reverse roll coater, a gravure coater, a micro-strip bar coater, a touch coater, a Maya coater (Meyer Coater), roller coaters such as air knife coaters, paddle coaters, etc. can be coated on the substrate and then dried by heating and ventilation ovens, vacuum dryers and other methods. Here, the 'supporting substrate is a film made of polyolefin such as polyethylene, polypropylene, 4-methyl-]-pentene copolymer, and release paper; a film made of release polyethylene terephthalate ; Films made of cellulose triacetate and so on. " 19- (15) 200401019 In order to peel the support substrate made of release paper and release polyethylene terephthalate, these release treatment surfaces are connected to this adhesive layer. Pressure molding by extrusion molding, co-extrusion molding, etc .; kneading; temperature when manufacturing the adhesive film or the adhesive laminated film, the temperature range necessary for performing these operations, and the adhesive composition of the present invention ( C) The temperature range where the component hardly foams, which is also below the decomposition temperature of the good component, specifically about 100 to 120 ° c. The layer of the laminated system of the present invention obtained by heating the adhesive film (hereinafter also referred to as This adhesive layer) and the adherend. In the case of an adhesive laminated film, the supporting substrate is generally peeled off and removed. The manufacturing method of the laminated body can be exemplified by a method of laminating an adherend on the side of the thin film layer of the adhesive laminated film, and peeling off the branch after being heated and adhered; a layer of the adhesive film of the adhesive laminated film Adhesive body 'method for heating the support substrate after peeling it off; laminating the adherend on the side of the adhesive film layer of the laminated film, and peeling the material on the peeling side of the supporting substrate, laminating it with the substrate The method of being adhered and heating. The heating temperature at the time of adhesion is generally lower than the decomposition temperature of the (C) component depending on the type of the (c) component used, specifically 80 ° C. The time can be appropriately determined within the range of confirming the state of being adhered upon heating and the component (c) does not decompose. The time can be at a higher temperature, or it can be performed at a lower temperature for a long time. In addition, the present invention can be predicted The adhesive resin composition is generally a sexual resin such as a gelled film and a self-drying film at a set temperature. (C) 〇 Adhesives use this specific adhesive to hold an adhesive support substrate on the substrate layer. However, it is easy to make a short-time confirmation time to 150 and the time required for -20- (16) 200401019 C) component foaming ', and the time required to prevent gelation and foaming is appropriately determined. Generally, it can be set at a temperature about 5 to 2 01: lower than the foaming temperature of the (C) component, and can be selected between about 5 to 60 minutes. When heating, the extruder can also be pressurized to about 1 to 6 MPa. The material constituting the adherend is a material that can be adhered to the adhesive layer. Specific examples include inorganic materials such as cellulose-based polymer materials, metals such as gold, silver, copper, iron, tin, 'lead, and silicon', and ceramics. ; Melamine-based tree 100% 'acrylic-urethane-based resin, urethane-based resin, (meth) acrylic-based resin, styrene-acrylonitrile-based copolymer, polycarbonate-based resin, Polymer materials such as phenol resins, alkyd resins, epoxy resins, and silicone resins. The material of the adherend may be a mixture of two or more different materials. In addition, if the laminated body is formed by two different adherends being adhered through the adhesive layer, the materials constituting the two adherends may be the same kind of materials or different kinds of materials. If the adherend has a heat-resistant temperature higher than the heating temperature at the time of peeling and recovering the adherend, it is preferable that the adherend is easily peeled from the interface between the adherend and the adhesive layer. m The laminated system thus obtained requires peelable and recyclable adherends, and can be used, for example, in refrigerators, washing machines, air conditioners, microwave ovens, vacuum cleaners, televisions, batteries and other household appliances; personal computers, printers, photocopiers, Office supplies such as fixed phones and mobile phones; buffers, battery containers and other daily necessities such as automobiles, furniture, and housing construction materials; liquid crystal panels, semiconductor 'printed circuit boards, integrated circuits, and secondary battery containers and other electronic products Π -21- (17) (17) 200401019 and others. Using an electronic product such as a semiconductor as an adherend, the adhesive laminated film of the present invention can also be used in a process release paper (primary adhesive protective paper) during manufacturing. By heating the laminated body of the present invention, the adherend can be easily peeled from the laminated body and recovered for recycling (reuse). For example, when the adhesive laminated film is used as an engineering release paper, an intermediate product composed of a laminated system engineering release paper (adhesive layer obtained by heating the adhesive film) and a product (adhered body) is not required. The product can be easily peeled and recovered by heating. The specific method for peeling and recovering the adherend is, for example, placing the laminated body in an oven, a warm water tank, etc., depending on the decomposition temperature of the foaming agent, which is generally about 80 to 300 ° C, which is better than A method of heating at about 120 to 240 ° C to foam (C) to peel off and recover the adherend; irradiate the laminate with flame, infrared, steam, ultrasonic waves, electromagnetic waves, etc., so that (C) A method of foaming to peel and recover an adherend; a method of placing a laminated body on a heating body such as an iron plate and foaming (C) to peel and recover an adherend. Either case can be appropriately combined to determine the sufficient temperature and time required for the (C) component to foam from the adhesive layer, for example, the foaming temperature of the (C) component is increased to a range of 2 < rc, 5 to 60 minutes Condition. The adherend recovered as described above can be easily peeled from the laminated body, and the adherend is not substantially attached with the substance originating from the adhesive layer, and even if the substance originating from the adhesive layer is attached, it is easy. Those who are peeled off from the adherend can recycle the adherend (reuse) or easily obtain a product. Recovered metals, plastics, and other adherends can also be melted and formed separately for reuse. -22-(18) (18) 200401019 The following examples illustrate the present invention in more detail, but the present invention is not limited thereto. Parts in the examples refer to weight basis unless otherwise specified.

,,, Γ b) and (C) components use the following. In addition, MFR (A), uv / 乂, and (MeH FI〇w Rate) are based on Japanese Industrial Standards (JIS, Japan.! S C a 1 e) K 7 2 1 0 at 19 ° C, 2 1 6 0 g load

Industrial. ; Fixed 値 ° (A) component A; "quick sticky C G 5 0 0 1" made by Sumitomo Chemical Industries, Ltd.,

Ethylene-methyl acrylate-glycidyl methacrylic acid copolymer, the content of the structural unit derived from glycidyl methacrylic acid is 1S by weight% MFR = 360g / 10 minutes (B) Component B: (Yes) Tefner's "Bendoine X 8 2 1 0", ethylene-ethyl acrylate-maleic acid copolymer, 6% by weight of structural unit derived from ethyl acrylate, structure derived from maleic anhydride Unit content 3% by weight, MFR = 200g /] 0 minutes (C) Component C: "Semaiku C--23- (19) (19) 200401019] 2 1" manufactured by Sankyo Chemicals Co., Ltd. , Azobiscarboxamide 'decomposition temperature 205 ° C, average particle size 10 to 14 β m. (Examples 1 to 3 and Comparative Example 1) (1): Production Example of Adhesive Resin Composition The above-mentioned A, B, and C were added to the small batch mixer "Laboratory Plastic Honing" in accordance with the weight ratios described in Table 1. ((Stock) Toyo Seiki Co., Ltd.'s main body: 50C150, mixer: Ri00H), under the condition that the drum setting temperature is 100, preliminary kneading is performed at 10 rpm for 7 minutes, and the main kneading is performed at 50 rpm 5 Minutes to obtain an adhesive resin composition. (2) Production Example of Adhesive Laminated Film (1) The obtained adhesive resin composition was hot-pressed according to the following preliminary molding conditions, 'on a hot plate of a hot-press machine preheated to 100 ° C. SUS board and fluororesin sheet were laminated in this order. On this fluororesin sheet, a polyethylene terephthalate base (Shoe) and the obtained preformed product were placed. Then, a fluororesin sheet was placed and then a SUS (stainless steel) sheet was placed. The following film forming conditions were followed by hot pressing to obtain an adhesive film. Next, the release surface of the film-shaped adhesive resin composition and the release film of the polyethylene terephthalate film "Enblade SC" (made by Neugeka) were overlapped. Using a laminator "¥ -800" (Dacheng Laminator (1 ^ 1 ^ 1131〇 | 〇 company), roll temperature: 80 ° C 'roll speed: 0.5m / min, roll pressure: 4.9x I04Pa -24- (20) (20) 200401019 (0.5kgf / cm2, gauge pressure reading) under conditions of heat lamination to obtain (supporting substrate: release polyethylene terephthalate film) / (adhesion Adhesive laminated film. <Pre-molding conditions> Wedge: 120mm x 120mm x] mm Thick hot plate Setting temperature: ° C, preheating I 〇min (3 punches) Pressing: 50kg / cm2x 1 Minutes—100kg / cm2x 1 minute-> 150kg / cm2, Cooling 100kg / cm2x2 Split canopy <Film forming conditions> Bottom pad · 150mm X 7 5mm x 0.1mm Thick hot plate Setting temperature: 1 〇 ° C, preheating for 10 minutes (3 times of punching) Pressure: 50kg / cm2x 1 minute—100kg / cm2x 1 minute- &gt; 1 5 Okg / cm2 'Cold Valley P 100kg / cm2x2 minutes (3) In the example, after cutting the adhesive laminated film obtained in (2) to a width of 25 mm, the square adhesive film is laminated on the SUS (stainless steel) plate or carrier glass as the adherend. That is, 'from below (supporting substrate) / (Adhesive film layer) / (adhered body) are laminated in the order. Then the support substrate is peeled off by hand, and then a polyethylene terephthalate film (PET film) without the following release treatment is laminated. After that, use a heat seal tester ("Heat Seal Tester τP-70] -B" manufactured by Tester Industry Co., Ltd.) to obtain (-25) (21) (21) 200401019 (base material) / (Adhesive film layer) / (adhered body) heat-sealed under pressure of 150 ° C, 9.8 X 1 0 4 P a (gauge pressure: 1 kgf / cm 2) for 30 minutes to obtain the invention Laminates ... The adherends used are the following items, and the (A) to (C) components and adherends contained in the adhesive resin composition used are shown in the table]. <Adhered Body> SUS: SUS304 Flat I60mmx 65mrnx 0.8mm thick carrier glass: made by MATSUNAMI (s) 1 1 26 76mmx 26mmx l.〇mm thick surface water mill <Base material> PET (Polyester) film: DI AF Ο IL T 6 0 0 E 5 0-W 0 7 5 0 μm thick Mitsubishi Chemical Polyester film double-sided coating film (4) before heating After measuring the laminated body obtained in (3) at a temperature of 23 ° C and a relative humidity of 50% for 1 hour, the test piece was cut into 10 mm wide X 100 mm long (adhesive length 25 mm) test pieces at a temperature of 2 3 The peeling test was performed at a peeling speed of 100 mm / sec and a peeling angle of 1 80 ° C under conditions of ° C and 50% relative humidity. -26- (22) (22) 200401019 (5) Force 卩 Thermal Peelability Test Place the laminated body prepared in (3) on a hot plate heated to 240 ° C, and place the adherend under it After heating for 5 minutes, observe its state. The results are shown in Table 1. The determination was made based on the following criteria. 〇: Immediately separated from the adherend. X: It is difficult to separate the adherend. Examples Comparative Examples 1 2 3 1 Adhesive tree A (parts) 4 8.5 47.6 46.3 50 Lipid composition B (parts) 48.5 47.6 46.3 50 Composition C (parts) 3.0 4. 8 7.4 0 C (phr) M 3 5 8 0 Adhesive force SUS (N / 10mm) 10.9 15.1 14.3 16.0 Glass (N / 10mm) 12.8 10.6 10.1 7.9 Thermal peelability 〇〇〇X peeling surface 112-100 parts C for A and B parts 1 The peeling of the interface between the adherend and the adhesive layer 2. The mixture of the peeling of the interface between the adherend and the adhesive layer, and the agglomeration and peeling of the adhesive layer. -27-(23) (23) 200401019 The adhesive film obtained by molding the adhesive resin composition of the present invention is a dry film type that is easy to store, handle, and workability before adhesion, and is adhered by heating. It then becomes an adhesive layer with superior adhesion. Therefore, in addition, it is easy to peel off and recover the adhered body with reduced adhesion only by heating. The recovered adhered body does not have an adhesive derived from an adhesive film, and even if it is attached, it is easily peeled from the adherend. To the extent that the adhered system is recyclable (recyclable). With such superior characteristics, the laminated body of the present invention can be used in, for example, packaging materials for electronic components such as semiconductor packaging materials, solar cells, or electroluminescence (EL) lamps, and die bonding sheets between integrated circuits / substrates. And the interlayer insulation layer between the substrates, the solder resist layer of the printed wiring board, the decorative film of automobile parts, plasma display devices, etc., or it can also be used as engineering release paper in semiconductor manufacturing. -28-

Claims (1)

200401019 Π) Pick up and apply for patent scope 1 '-a composition containing the following (A), (B) and resin composition: (A): olefin resin containing epoxy groups, (B): hardener (C) thermal decomposition type Foaming agent. 2. As for the "(A)" component in the scope of the patent application, the component (A) is the following (a,) and (a2-based ethylene j · Hexyl copolymers): () At least one ethylene (a 2) is selected from the following general formula (The group consisting of monomers represented by the following general formula (2) R Ο / CH2 X 'ch2-ch ο (where R represents a carbon number of 2 having a double bond and a group of 2 can also be combined with a halogen atom, and X represents a single bond Or carbonyl r—o-co-ch2-ch ^ I \ 〇 (In the formula, IT indicates that a carbon number of 2 having a double bond can be combined with a halogen atom, and Y indicates a carbonyl group. Or the first product, in which the component (A) is an adhesive resin composition that does not react with the epoxy group. (C) the monomer contains an epoxy-containing monomer shown in 1) and a monomer obtained by polymerization. Hydrocarbon group to 18, the hydrocarbon group), (2) to 18 hydrocarbon group, and the adhesive resin group of the hydrocarbon item 2 can be copolymerized with ethylene -29- (2) (2) 200401019 monomer, the above (a !) Monomers and copolymers obtained by polymerizing (a2) monomers. 4. For the adhesive resin composition according to any one of claims 1 to 3 in the scope of patent application, wherein (B) component is the following ethylene obtained by polymerization of (b 1), (b2), and (b 3) · a, yS-unsaturated carboxylic acid copolymer (b 1) ethylene '(b2) α, / 3-unsaturated carboxylic acid and / or β, / 3-unsaturated carboxylic anhydride, (b3) vinyl ester and / or α , Million-unsaturated carboxylic acid ester. 5. The adhesive resin composition according to item 4 of the scope of the patent application, wherein the (B) component is the total amount of the entire structural unit constituting the (B) component] 0 0 parts by weight and contains a monomer derived from (b 2) The structural unit is 0.0 1 to 20 parts by weight, and the structural unit derived from (b3) monomer is 25 to 70 parts by weight. 6. The adhesive resin composition according to any one of claims 1 to 5 of the scope of patent application, wherein the component (A) is an epoxy group-containing polymer obtained by polymerizing the polymer (a!) And the polymer (a 2). (B) component is an ethylene · α, / 3-unsaturated carboxylic acid copolymer obtained by polymerizing the above (bl), (b2), and (b3) above, and has a structure derived from ethylene. A unit whose total content is 30 to 75 parts by weight based on 100 parts by weight of the total amount of the (A) component and the (B) component. 7. The adhesive resin composition according to any one of claims 1 to 6 in the scope of patent application, wherein the weight ratio of the component (A) to the component (B) is (A) / (B) = 90/10 To 40/60. -30- (3) (3) 200401019 8. The adhesive resin composition according to any one of claims 1 to 7 of the scope of application for patents, wherein the component (C) is azobiscarboxamide. 9. The adhesive resin composition according to any one of the scope of the patent application item No. 8 to No. 8, wherein 100 parts by weight of the total amount of the component (A) and the component (B) contains (C) Ingredients are 2 to 10 parts by weight. 10 — An adhesive film, which is formed by forming a thin film of the adhesive resin composition according to any one of the scope of the patent application from item No.9 to item No.9. 1 1. The adhesive film according to item 10 of the scope of patent application is obtained by pressure-molding the kneaded material obtained by kneading the adhesive resin composition. ] 2. If the adhesive film of the scope of application for item 10 is obtained by dissolving or dispersing the adhesive resin composition in a solvent, coating it on a flat surface and drying it. ] 3. A kind of adhesive laminated film, which is formed by laminating an adhesive film in any one of the patent scopes Nos. 10 to 12 on a supporting substrate. 1 4 · The adhesive laminated film according to item I 3 of the patent application scope, wherein the 'supporting substrate is at least one selected from the group consisting of a polyolefin film, a release polyethylene terephthalate film, and triacetic acid. Films made of cellulose and release paper. 1. A kind of laminated body, which is composed of an adhesive layer and an adherend obtained by heating an adhesive film according to any one of the scope of application patents No. 10 to No. [2]. 1 6. —A laminated body with an adhesive layer and an adherend is an adhesive film whose adhesive volume layer is No. 13 or No. 4 in the scope of patent application -31-(4) (4) 200401019 Adhesive resin composition is formed into a thin film on the side of an adhesive layer, and the laminate is heated and adhered at a temperature lower than the decomposition temperature of the component (C), and the support substrate is peeled off. 1 7. ~ A laminated body having an adhesive layer and an adherend, which is formed by thinning an adhesive resin composition having an adhesive volume layer in an adhesive film in the scope of patent application No. 13 or 14 It is obtained by heating and sticking the support substrate below the decomposition temperature of the component (C) after the support substrate is peeled off from the adhesive layer side. 1 8 .—A laminated body having an adhesive layer and an adherend, which is formed by thinning an adhesive resin composition of the adherent volume layer in the adhesive film of item 3 or 14 of the scope of the patent application. The adhesive layer side and the support substrate is peeled off, then the adherend on the release surface side of the support substrate is laminated with an adherend which is different from the adherend and is heated and adhered below the decomposition temperature of the component (C) . 1 9. A method for recovering adherends, which is characterized in that it will apply for patents ranging from 15th to 15th! The laminated body according to any one of 8 items, which is heated above the decomposition temperature of the component (c) to peel off the adherend from the laminated body. -32-200401019 Lu, (1) The designated representative of this case is: None. (2) Brief description of the representative symbols of the elements in this case: None. If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: None