JP2021059709A - Adhesive resin composition - Google Patents

Abstract

To provide an adhesive resin composition that is free of a volatile organic compound and has sufficient adhesiveness and flexibility.SOLUTION: An adhesive resin composition contains a urethane-acryl composite resin (C) with a urethane unit (A) and a (meth) acryl unit (B) coupled with a chain transfer agent residue, a curing agent (D), and a reactive diluent (E). The (meth) acryl unit (B) has a constitutional unit derived from an ethylenic unsaturated monomer (G) having an epoxy group.SELECTED DRAWING: None

Description

In the present invention, the urethane / acrylic composite resin (C), the curing agent (D), and the reactive diluent () in which the urethane unit (A) and the (meth) acrylic unit (B) are linked by the residue of the chain transfer agent (C). An adhesive resin composition (F) containing E), wherein the (meth) acrylic unit (B) has a structural unit derived from an ethylenically unsaturated monomer (G) having an epoxy group. The adhesive resin composition (F) to be used.

In the fields of automobiles, building materials, ships, aircraft, etc., various structural adhesives are used to bond and fix metals such as resin, glass, iron, aluminum, and stainless steel, and ceramics. In recent years, in the fields of automobiles and aircraft, weight reduction has been promoted to improve fuel efficiency, the ratio of materials made of plastic and fiber reinforced plastic (hereinafter referred to as FRP) has been increased, and metal is made lighter than iron. There is an active movement to replace these with aluminum, and there is a demand for an adhesive that can firmly bond these. Further, from the viewpoint of workability and reduction of environmental load, an adhesive containing no volatile organic compounds is required.

However, for example, when a metal such as aluminum and a material having a different linear expansion coefficient such as FRP are bonded to each other, a high stress is applied to the adhesive layer due to the difference in expansion coefficient between the materials caused by the temperature change in the manufacturing process or the operating temperature environment. , There is a problem of accelerating the destruction or deterioration of the adhesive layer.

In response to such problems, for example, in Patent Documents 1 to 3, there is a method of adding long-chain polyamines, nano-dispersed rubber-like particles, or the like to an epoxy compound having high adhesiveness to metals or FRP for the purpose of stress relaxation. Proposed. However, although these methods can impart a certain degree of flexibility, the obtained adhesive layer is still hard and brittle, and the effect is not sufficient.

Special table 2018-506635 International Publication No. 2007/025007 JP 2015-182248

An object of the present invention is to provide a structural adhesive suitable for the fields of automobiles, building materials, ships, aircraft, etc., which does not contain volatile organic compounds and has sufficient adhesiveness and flexibility.

Contains a urethane-acrylic composite resin (C), a curing agent (D), and a reactive diluent (E) in which the urethane unit (A) and the (meth) acrylic unit (B) are linked by a residue of a chain transfer agent. The adhesive resin composition (F) to be used, wherein the (meth) acrylic unit (B) has a structural unit derived from an ethylenically unsaturated monomer (G) having an epoxy group. With respect to composition (F).

The present invention relates to the above-mentioned adhesive resin composition (F), wherein the urethane unit (A) and the (meth) acrylic unit (B) are linked by a residue of a chain transfer agent having an amino group.

The claim is characterized in that the content of the structural unit derived from the ethylenically unsaturated monomer (G) having an epoxy group is 5 to 100 parts by weight out of 100 parts by weight of the (meth) acrylic unit (B). Item 2. The adhesive resin composition (F) according to Item 1 or 2.

The invention according to any one of claims 1 to 3, wherein the content of the (meth) acrylic unit (B) is 10 to 60 parts by weight out of 100 parts by weight of the urethane / acrylic composite resin (C). The adhesive resin composition (F) of the above.

The present invention relates to a laminate formed by using the resin composition (F) described above.

INDUSTRIAL APPLICABILITY According to the present invention, it has been possible to provide a structural adhesive suitable for fields such as automobiles, building materials, ships, and aircraft, which does not contain volatile organic compounds and has sufficient adhesiveness and flexibility.

The adhesive resin composition (F) of the present invention contains a urethane-acrylic composite resin (C), a curing agent (D), and a reactive diluent (E).

<Urethane / acrylic composite resin (C)>
The urethane-acrylic composite resin (C) of the present invention has a structure in which the urethane unit (A) and the (meth) acrylic unit (B) are linked by a chain transfer agent residue, and the (meth) acrylic unit (B). ) Has a structural unit derived from an ethylenically unsaturated monomer (G) having an epoxy group.

The urethane / acrylic composite resin (C) can be produced by the following method. First, a chain transfer agent having an isocyanate group in a urethane prepolymer having an isocyanate group at both ends, which is obtained by reacting a polyol and an isocyanate group-containing compound, and a functional group and a mercapto group capable of reacting with the isocyanate group in the molecule. To synthesize a urethane unit (A) having a mercapto group, which is a chain transfer agent residue, at both ends. Then, using the terminal mercapto group in the obtained urethane unit (A), the ethylenically unsaturated monomer containing the ethylenically unsaturated monomer (G) having an epoxy group was chain-transfer polymerized (meth). ) Form an acrylic unit (B). In this way, the urethane-acrylic composite resin (C) in which the urethane unit (A) and the (meth) acrylic unit (B) are linked by a chain transfer agent residue can be obtained. All of these reactions may be carried out using a solvent, but when a solvent is used, the solvent is removed at the intermediate stage of the reaction or after the reaction is completed under reduced pressure or normal pressure.

First, the urethane unit (A) of the urethane / acrylic composite resin (C) will be described below.

<Polyprethane>
Typical examples of the polyols constituting the urethane unit (A) include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, vegetable oil-based polyols, and other polyols. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the polyether polyol include polymers or copolymers such as methylene oxide, ethylene oxide, propylene oxide and tetrahydrofuran, specifically, polyethylene glycol, polypropylene glycol, poly (ethylene / propylene) glycol and polytetramethylene glycol. And so on. Further, examples thereof include hexanediol, methylhexanediol, heptanediol, octanediol, and polyether polyols obtained by condensing a mixture thereof.

Further, as the polyether polyol, a compound having at least two or more active hydrogen groups such as a low molecular weight polyol, an aliphatic amine compound, an aromatic amine compound, an alkanolamine, and a bisphenol is used as a starting material. Examples thereof include a polyol obtained by adding an alkylene oxide such as methylene oxide, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, or polyoxytetramethylene oxide.

Among the compounds having two or more active hydrogen groups, examples of the low molecular weight polyol include a bifunctional low molecular weight polyol and a trifunctional or higher functional low molecular weight polyol.

The bifunctional low molecular weight polyol is not particularly limited, but for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4. -Butanediol, neopentyl glycol, pentandiol, hexanediol, octanediol, nonanediol, dipropylene glycol, diethylene glycol, triethylene glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1 , 3-Propanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, polyoxyethylene glycol (additional moles: 10 or less), polyoxypropylene glycol (additional moles: 10 or less) ), Cyclohexanediol, Cyclohexanedimethanol, Tricyclodecanedimethanol, Cyclopentadienedimethanol, Dimerdiol, Bisphenol A, N, N-bis (2-hydroxypropyl) aniline, Dimethylolacetic acid, Dimethylolpropionic acid, Dimethylolbutane Acids, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, dihydroxysuccinic acid, dihydroxypropionic acid, dihydroxybenzoic acid and the like can be mentioned.

The trifunctional or higher functional low molecular weight polyol is not particularly limited, but is limited to trimethylolethane, trimethylolpropane, 1,1,1-trimethylolbutane, 1,2,3-butanetriol, 1,2,4-butanetriol. , 1,2,6-butanetriol, trimethylolpropane, trimethylolpentene, trimethylolhexene, trimethylolhepten, trimethylolocten, trimethylolnonen, trimethylolpropane, trimethylolpropane, trimethylolpropane, tri Methylolpropane, trimethylolpentadecene, trimethylolhexadecene, trimethylolheptadecene, trimethyloloctadecene, 1,1,1-trimethylol-2-methyl-hexane, 1,1,1-trimethylol-3-methyl -Hexane, 1,1,1-trimethylol-2-ethyl-hexane, 1,1,1-trimethylol-3-ethyl-hexane, trimethylolhexene, 1,2,3-octanetriol, 1,3 7-octanetriol, 3,7-dimethyl-1,2,3-octanetriol, 1,1,1-, 1,1,1-trimethylolpropane, 1,2,10-decantryol, 1,1, 1-trimethylolisoheptadecane, 1,1,1-trimethylol-sec-butane, 1,1,1-trimethylol-tert-pentane, 1,1,1-trimethylol-tert-nonan, 1,1 , 1-trimethylol-tert-tridecane, 1,1,1-trimethylol-tert-heptadecane, 1,1,1-trimethylol-2-methyl-hexane, 1,1,1-trimethylol-3-methyl -Hexane, 1,1,1-trimethylol-2-ethyl-hexane, 1,1,1-trimethylol-3-ethyl-hexane, 1,1,1-trimethylolisoheptadecane, 1,2,3 , 4-Butantetraol, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin, triglycerin, polyglycerin, trimethylolethane, dimethylolpropane, tris (2-hydroxyethyl) isocyanurate, benzene-1 , 3,5-Triol, benzene-1,2,3-triol, Stilben-3,4', 5-Triol, shoe claus, inositol, sorbitan, sorbitol, mannitol, saccharose, cellulose, xylitol Le etc. can be mentioned.

Among the compounds having two or more active hydrogen groups, examples of the aliphatic amine compounds include ethylenediamine, triethylenetetramine, diethylenetriamine, and triaminopropane. Examples of aromatic amine compounds include toluenediamine, diphenylmethane-4,4-diamine and the like. Examples of alkanolamines include ethanolamine and diethanolamine. Examples of bisphenols include bisphenol A, bisphenol AP, bisphenol B, bisphenol C, bisphenol E, bisphenol F and the like.

Examples of the polyester polyol include a polyester polyol in which the above-mentioned low molecular weight polyol and a dibasic acid component are condensed and reacted.

Examples of the dibasic acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, hydrogenated dimer acid, phthalic anhydride, isophthalic acid, trimellitic acid, glutaric acid, pimeric acid, suberic acid, and sebacic acid. Lipid or aromatic dibasic acids, and their anhydrides.
Examples thereof include polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones such as ε-caprolactone, poly (β-methyl-γ-valerolactone) and polyvalerolactone.

Examples of the polycarbonate polyol include those obtained by reacting the above-mentioned low molecular weight polyol with a carbonate compound such as dialkyl carbonate, alkylene carbonate, and diaryl carbonate.
Further, examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate and the like, examples of the alkylene carbonate include ethylene carbonate and the like, and examples of the diaryl carbonate include diphenyl carbonate and the like.

Examples of the polyolefin-based polyol include hydroxyl group-containing polybutadiene, hydrogenated hydroxyl group-containing polybutadiene, hydroxyl group-containing polyisoprene, hydrogenated hydroxyl group-containing polyisoprene, hydroxyl group-containing chlorinated polypropylene, and hydroxyl group-containing chlorinated polyethylene.

Examples of the vegetable oil-based polyol include castor oil derived from plants, dimer acid, and polyols made from soybean oil.

Among these, a polyether polyol, a polyester polyol, and a polycarbonate polyol are preferable, and a polyether polyol is more preferable.

The molecular weight of these polyols is preferably 500 or more and less than 5000, and more preferably 700 or more and less than 3,500 in terms of number average molecular weight.

Further, the above-mentioned low molecular weight polyol can be used in combination for the purpose of adjusting the urethane bond concentration and introducing various functional groups.

<Isocyanate group-containing compound>
Examples of the isocyanate group-containing compound constituting the urethane unit (A) include aromatic, aliphatic, and alicyclic isocyanate group-containing compounds. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the aromatic isocyanate group-containing compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylenedi isocyanate, p-phenylenedi isocyanate, 4,4'-diphenylmethane diisocyanate, and 2,4-diphenylmethane. Diisocyanate, 2,2'-diphenylmethane diisocyanate, 1,5-naphthalenediocyanate, trizine diisocyanate, xylylene diisocyanate, m-tetramethylxylene diisocyanate, p-tetramethylxylene diisocyanate, 3,3'- Dimethyl-4,4'-biphenylenediocyanate, 3,3'-dimethoxy-4,4'-biphenylenediocyanate, 3,3'-dichloro-4,4'-biphenylenediocyanate, 1,5-tetrahydronaphthalenediisocyanate and the like. Be done.

Examples of the aliphatic isocyanate group-containing compound include trimethylene diisocyanis, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanis, 2,3-butylenedisocyanate, 1,3-butylenedisocyanate, and dodecamethylene. Diisocyanate, 2,4,4-trimethylhexamethylene diisocyanis, lysine diisocyanis, lysine ester triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate tetramethylene diisocyanate, pentamethylene diisocyanate, Examples thereof include trimethylhexamethylene diisocyanate.

Examples of the alicyclic isocyanate group-containing compound include isophorone diisocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, and methyl-2. Examples thereof include 6-cyclohexanediisocyanate, 4,4′-methylenebis (cyclohexylisocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, hydrogenated xylylene diisocyanate, diisocyanate dimerate, and norbornene diisocyanate.

The reaction between the polyol and the isocyanate group-containing compound is preferably carried out in a solvent-free environment using a known urethanization reaction. A catalyst may be used for the purpose of adjusting the reactivity.

<Catalyst>
As the catalyst, known metal-based catalysts and amine-based catalysts can be used. Metallic catalysts include dibutyltin dilaurate, tin octoate, dibutyltin di (2-ethylhexoate), lead 2-ethylhexoate, 2-ethylhexyl titanate, titanium ethylacetate, 2-ethylhexoate. Examples thereof include iron, 2-ethylhexoate cobalt, zinc naphthenate, cobalt naphthenate, tetra-n-butyltin and the like. Examples of the amine-based catalyst include tertiary amines such as tetramethylbutanediamine. These catalysts are preferably in the range of 0.05 to 1 mol% with respect to the polyol.

<Number average molecular weight of urethane unit (A)>
The number average molecular weight of the urethane unit (A) is not particularly limited, but is preferably 3,000 to 200,000.

<Chain transfer agent>
As the chain transfer agent of the present invention, a chain transfer agent having a mercapto group is preferable.
A chain transfer agent having a mercapto group serving as a connecting site between the urethane unit (A) and the (meth) acrylic unit (B) of the urethane-acrylic composite resin (C) will be described below.

<Chain transfer agent with mercapto group>
The chain transfer agent having a mercapto group is not particularly limited as long as it has a functional group capable of reacting with an isocyanate group and a mercapto group in the molecule, but preferably one amino group and one mercapto in the molecule. It is a compound having a group. The mercapto group also has reactivity with the isocyanate group, but by having an amino group in the molecule that is more reactive than the mercapto group, the amino group quickly reacts with the isocyanate group in the urethane prepolymer, and the urethane prepolymer The mercapto group is efficiently introduced at the terminal.

Compounds having one amino group and one mercapto group in the molecule are not limited, for example, 2-aminoethanethiol, 3-aminopropyl-1-thiol, 1-aminopropyl-2-thiol, 4-. Amino alkanethiols such as amino-1-butanethiol;
Examples thereof include aminobenzenethiols such as 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Of these, 2-aminoethanethiol is preferable.

Next, the (meth) acrylic unit (B) of the urethane-acrylic composite resin (C) will be described below. The (meth) acrylic unit (B) has a structural unit derived from an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer (G) having an epoxy group.

As a method for constructing the (meth) acrylic unit (B) from the urethane unit (A) having a mercapto group which is a chain transfer agent residue at both ends, an epoxy is used by using the terminal mercapto group in the urethane unit (A). A (meth) acrylic unit (B) is formed by performing chain transfer polymerization of an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer (G) having a group in the presence of a polymerization initiator.

<Epoxy unsaturated monomer (G)>
The ethylenically unsaturated monomer (G) having an epoxy group is not limited to the following examples, but a compound having one polymerizable unsaturated double bond and one or more epoxy groups in the molecule is used. It can be used, for example, glycidyl (meth) acrylic acid, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7. -Epoxide pentyl, (meth) acrylic acid-3,4-epoxide cyclohexyl, 4-hydroxybutyl acrylate glycidyl ether, lactone-modified (meth) acrylic acid-3,4-epoxide cyclohexyl, vinylcyclohexene oxide and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The ethylenically unsaturated monomer (G) having an epoxy group preferably contains 5 to 100 parts by weight, more preferably 10 to 100 parts by weight, out of 100 parts by weight of the (meth) acrylic unit (B). It is preferable that the ethylenically unsaturated monomer (G) having an epoxy group is 5 to 100 parts by weight because it is excellent in adhesive strength and flexibility.

The (meth) acrylic unit (B) may contain other ethylenically unsaturated monomers in addition to the ethylenically unsaturated monomer (G) having an epoxy group.

Other ethylenically unsaturated monomers include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl. (Meta) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate , Decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, etc. Alkylethylene unsaturated monomers;
Cyclohexyl (meth) acrylate, tertiary butyl cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) ) Cyclic alkyl (meth) acrylates such as acrylates and isobornyl (meth) acrylates;
Fluoroalkyl ethylenically unsaturated monomers such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate;
Ethylene unsaturated monomers having a heterocycle such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;
Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meta) acrylates having an aromatic ring of
Methoxypolyethylene glycol mono (meth) acrylate, octoxypolyethylene glycol polypropylene glycol mono (meth) acrylate, lauroxypolyethylene glycol mono (meth) acrylate, stearoxypolyethylene glycol mono (meth) acrylate, phenoxypolyethylene glycol mono (meth) acrylate, Phenoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, nonylphenoxy polyethylene glycol mono (meth) acrylate, nonylphenoxypolyethylene glycol mono (meth) acrylate, Nonylphenoxypolyethylene glycol polypropylene glycol mono (meth) acrylate, phenoxypolyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, n-butoxyethyl (meth) acrylate, n-butoxydiethylene glycol (meth) acrylate, 2-methoxy Ethethylene unsaturated monomers having an alkyl ether group such as ethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate;
3- (Acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- Oxetanyl groups such as (acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (methacryloyloxymethyl) 3-hexyloxetane Ethylity unsaturated monomers having;
Ethylene unsaturated monomers having a vinyl group such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, or allyl (meth) acrylate;
Ethyl unsaturated monomers having an ether group such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;
2-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2 -Hydroxy-3-allyloxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate or caprolactone adducts of these monomers (additional moles 1-5), polyethylene glycol (meth) acrylate , Polypropylene glycol (meth) acrylate, glycerin mono (meth) acrylate and other ethylenically unsaturated monomers having hydroxyl groups;
Ethylene unsaturated monomers having a carboxyl group such as (meth) acrylic acid, itaconic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyhexahydrophthalic acid, etc. ;
Aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, methyl Ethylaminoethyl (meth) acrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, N , N-diethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylthiopyrrolidone, N-vinylpyrrole Amino group-containing ethylenically unsaturated monomers such as salts thereof;
(Meta) Cyan group-containing ethylenically unsaturated monomers such as acrylonitrile, cyanostyrene, and cyanoacrylate;
(Meta) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) Acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N -Vinylpyrrolidone, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) metaacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) metaacrylamide, Amide group-containing ethylenically unsaturated monomers such as N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) metaacrylamide, and cinnamic acid amide;
Trimethylammonioethyl (meth) acrylate chloride, methyldiethylammonioethyl (meth) acrylate bromide, trimethylammonioethyl (meth) acrylamide methacrylamide, benzyldiethylammonioethyl (meth) acrylamide carbonate, dimethyldialylammonium chloride, trimethylallyl Ethyl unsaturated monomers containing quaternary ammonium cations such as ammonium chloride;
Ethylene unsaturated monomers having a keto group such as acrolein, methacrolein, diacetone acrylamide, diacetone methacrylamide, vinyl methyl ketone, vinyl ethyl ketone, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, and formyl styrene are used. Can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The (meth) acrylic unit (B) preferably contains 10 to 60 parts by weight, more preferably 15 to 40 parts by weight, out of 100 parts by weight of the urethane / acrylic composite resin (C). It is preferable to include the (meth) acrylic unit (B) in an amount of 10 to 60 parts by weight because it is excellent in flexibility and adhesive strength.

<Polymerization initiator>
A known azo-based compound or organic peroxide can be used as the polymerization initiator, and the azo-based compound is not limited to the following examples, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'- Azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 1,1'-azobis (1-cyclohexanecarboxylate) , Dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), or 2 , 2'-azobis [2- (2-imidazolin-2-yl) propane] and the like, and examples of the organic peroxide are not limited to the following examples, but for example, benzoyl peroxide and t-butylperoxy. 2-ethylhexaate, t-butylperbenzoate, cumenehydroperoxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, t-butylper Oxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The polymerization initiator is preferably used in the range of 0.001 to 15 parts by weight with respect to 100 parts by weight of the (meth) acrylic unit (B). A range of 0.001 to 15 parts by weight is preferable because chain transfer polymerization effectively proceeds.

<Number average molecular weight of (meth) acrylic unit (B)>
The number average molecular weight of the (meth) acrylic unit (B) is not particularly limited, but is preferably 2,000 to 200,000.

<Number average molecular weight of urethane / acrylic composite resin (C)>
The number average molecular weight of the urethane-acrylic composite resin (C) is not particularly limited, but is preferably 5,000 to 300,000.

<Solvent>
Examples of the solvent include ethers such as dibutyl ether, dimethoxymethane, dimethoxyethane, propylene oxide, 1,3-dioxolane, 1,4-dioxane, and tetrahydrofuran;
Esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate;
In addition to ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, toluene, methylcyclohexane, acetonitrile and the like can be mentioned. These solvents may be used alone or in combination of two or more.

<Curing agent (D)>
The curing agent (D) is not particularly limited, and a known curing agent that cures the epoxy resin can be used, and examples thereof include amine compounds, amide compounds, acid anhydrides, and phenol resins.

Amine compounds include ethylenediamine, diaminopropane, diaminobutane, diaminohexane, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylene. Aliper amines such as pentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine polyethyleneimine dimer acid ester;
Isophorone diamine, metacene diamine, N-aminoethyl piperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-aminopropyl) 2,4,8, Alicyclic amines such as 10-tetraoxaspiro (5,5) undecane, norbornenediamine, bis (aminomethyl) norbornan, bis (4-aminocyclohexyl) methane;
Tetrachloro-p-xylene diamine, m-xylene diamine, p-xylene diamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanizole, 2,4-toluenediamine, 2, 4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diamino Diphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (m-aminophenyl) ethylamine, α- (p-amino) Phenyl) ethylamine, diaminodiethyldimethyldiphenylmethane, α, α'-bis (4-aminophenyl) -p-diisopropylbenzene, 3,3'-diisopropyl-4,4'-diaminodiphenylmethane, 3,3'-di-t -Butyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, N, N-dimethylaniline, N, N-dimethylbenzylamine, 2, Aromatic amines such as 4,6-tris (dimethylaminomethyl) phenol;
2-Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2,4-diethylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, etc. Imidazole derivatives of
Boron trifluoride-amine complexes such as boron trifluoride-monoethylamine, boron trifluoride-piperidin, boron trifluoride-triethylamine, boron trifluoride-aniline complex;
Diciandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, toluruguanidine, 2,3-guanylurea, benzoyldiciandiamide, 2,6-xylenylbiguanide, phenylbiguanide Guanidine derivatives such as: triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), poly (propylene glycol) diamine, poly (propylene glycol) triamine, poly (ethylene glycol) diamine, poly (ethylene). Polyether polyamines such as glycol) triamine, poly (tetramethylene ether glycol) diamine, poly (tetramethylene ether glycol) triamine, poly (propylene / ethylene glycol) diamine, poly (propylene / ethylene glycol) triamine, etc. be able to. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the amide compound include polyamide amine having a primary amine and a secondary amine in the molecule, which is formed by reacting a dimer of linolenic acid or oleic acid with a polyamine such as diethylenetriamine or triethylenetetramine. Can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydro. Examples include phthalic anhydride. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phenol resin include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin (Zyroc resin), and resorcin novolac resin. Polyvalent phenol novolac resin synthesized from hydroxy compound and formaldehyde, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl Modified phenol resin (polyvalent phenol compound in which phenol nuclei are linked by bismethylene group), biphenyl-modified naphthol resin (polyvalent naphthol compound in which phenol nuclei are linked by bismethylene group), aminotriazine-modified phenol resin (melamine, benzoguanamine, etc.) Examples thereof include polyvalent phenol compounds in which phenol nuclei are linked) and polyvalent phenol compounds such as an alkoxy group-containing aromatic ring-modified novolak resin (polyphenol compounds in which a phenol nuclei and an alkoxy group-containing aromatic ring are linked with formaldehyde). .. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Among these, dicyandiamide is preferable because it has a long pot life and high adhesive strength can be obtained.

The ratio of the total number of moles of all epoxy groups contained in the adhesive resin composition (F) to the total number of moles of active hydrogen groups involved in the reaction with the epoxy groups in the curing agent (D) (epoxide group / The active hydrogen group) in the curing agent is preferably 0.5 to 1.5 because it is excellent in extensibility, adhesive strength and flexibility.

<Reactive diluent (E)>
The reactive diluent (E) is not particularly limited as long as it is a compound having a bifunctional or higher functional epoxy group, and a compound having a known epoxy group can be used.
The reactive diluent (E) is preferably in a liquid state at room temperature. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol AD type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, alicyclic epoxy resin, glycidyl ester. Examples thereof include based epoxy resins, heterocyclic epoxy resins, diarylsulfone type epoxy resins, hydroquinone type epoxy resins, and modified products thereof. Examples of the trifunctional or higher functional epoxy resin include glycidylamine-based epoxy resin, naphthalene type epoxy resin, novolac type epoxy resin, and polyfunctional glycidyl ether. One of these may be used alone, or two or more thereof may be used.

<Adhesive resin composition (F)>
The adhesive resin composition (F) in the present invention is obtained by mixing a urethane-acrylic composite resin (C), a curing agent (D), and a reactive diluent (E) by a known method. In addition to these, curing accelerators, silane coupling agents, leveling agents or antifoaming agents, fillers, propellants, plasticizers, superplasticizers, wetting agents, flame retardants, viscosity modifiers, preservatives, stabilizers and A known additive such as a colorant may be blended and used.

When dicyandiamide is used as a curing agent, examples of the curing accelerator include 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 2-ethyl-2-phenylimidazole. , 1-Cyanoethyl-2-ethyl-4-methylimidazole and other imidazole compounds;
Tertiary amine compounds such as triethylamine and 2,4,6-tris (dimethylaminomethyl) phenol, boron trifluoride / piperidine complex, boron trifluoride / monoethylamine complex, boron trifluoride / triethanolamine complex, trifluoride Lewis acid complexes such as boron halide such as boron chloride / octylamine complex;
Onium salts such as ammonium salts and phosphonium salts; N, N-dimethyl-N'-(3-chloro-4-methylphenyl) urea, N, N-dimethyl-N'-(4-chlorophenyl) urea, N, N -Dimethyl-N'-(3,4-dichlorophenyl) urea, N, N-dimethyl-N- (3,4-dichloromethylphenyl) urea, 2,4- (N', N'-dimethylureide) toluene , 1,4-Bis (N', N'-dimethylureido) benzene and other urea derivatives, as well as dicyandiamide derivatives. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The amount of the reaction accelerator added is preferably 0.005 to 5 parts by weight with respect to 100 parts by weight of the solid content of the urethane-acrylic composite resin (C) in the adhesive resin composition (F).

Examples of the silane coupling agent include trialkoxysilanes having a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-aminopropyltriethoxysilane, and N- (2-aminoethyl) 3-aminopropyltrimethoxysilane. Trialkoxysilanes having amino groups such as 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilanes, 3-glycidoxypropyltriethoxysilanes and the like having glycidyl groups. Examples thereof include trialkoxysilane having an isocyanate group such as trialkoxysilane and 3-isocyanatepropyltriethoxysilane, and trialkoxysilane having a mercapto group such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The amount of the silane coupling agent added is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the solid content of the urethane-acrylic composite resin (C) in the adhesive resin composition (F).

Among the leveling agents or defoaming agents, examples of the leveling agent include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, and polyether ester-modified hydroxyl group. Examples thereof include polydimethylsiloxane, acrylic copolymer, methacrylic copolymer, polyether-modified polymethylalkylsiloxane, acrylic acid alkyl ester copolymer, methacrylic acid alkyl ester copolymer, and lecithin.

Examples of the defoaming agent include known ones such as a silicone resin, a silicone solution, and a copolymer of an alkyl vinyl ether, an acrylic acid alkyl ester, and a methacrylic acid alkyl ester.

<Laminated body>
The laminate of the present invention is not particularly limited as long as it contains an adhesive layer made of the adhesive resin composition (F), and can be formed by using a known lamination method. The adhesive resin composition (F) is applied to one surface to form an adhesive layer, and then another base material is superposed on the adhesive layer before the curing treatment, and the adhesive is applied under the condition of about 20 to 150 ° C. By curing the layer, a laminate composed of a base material and an adhesive layer can be obtained. The film thickness of the adhesive layer is preferably 0.1 μm to 300 mm.

The adhesive resin composition (F) of the present invention can be used on many substrate surfaces. Suitable substrates include, but are not limited to, metals such as aluminum, thermoplastic polymers such as polyethylene, polylopylene, polyurethane, polyacrylates and polycarbonates and their copolymers, thermosetting polymers such as vulture rubber, Urea-formaldehyde foam, melamine resin, wood, carbon fiber reinforced plastics, glass fiber reinforced plastics and other fiber reinforced plastics, etc., and the same, similar or different base materials can be bonded to these base materials. ..

The laminate produced by using the adhesive resin composition (F) of the present invention can be used for automobiles, building materials, ships, etc. because the adhesive resin composition (F) of the present invention has sufficient adhesiveness and flexibility. It is useful as a structural member (panel parts, skeleton parts, undercarriage parts, etc.) of transportation equipment such as aircraft.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples do not limit the scope of rights of the present invention at all. Unless otherwise specified, "parts" in the examples represent "parts by weight" and "%" represents "% by weight".

The number average molecular weight in the examples was converted to polystyrene when Shodex GPCLF-604 (manufactured by Shodex) was used as a column and THF was used as a developing solvent in a GPC (manufactured by Shodex, GPC-104) equipped with an RI detector. The molecular weight was used.

[Manufacturing Example 1]
In a reaction vessel equipped with a nitrogen gas introduction pipe, a stirrer, a thermometer, and a recirculator, first, as a polyol, 100 parts of P-1000 (product name, general name: bifunctional polypropylene glycol, hydroxyl value 110, manufactured by ADEKA), isocyanate. 28.3 parts of isophorone diisocyanate as a group-containing compound and 0.02 parts of titanium diisopropoxybiz (ethylacetoacetate) as a reaction accelerator were charged and uniformly stirred, and then reacted at 110 ° C. for 5 hours in a nitrogen atmosphere to make a urethane prepolymer. Got Next, the mixture was cooled to 80 ° C., 69.9 parts of methyl ethyl ketone was added as a solvent, 2.2 parts of 2-aminoethanethiol was added as a chain transfer agent, and the mixture was reacted at 75 ° C. for 2 hours to obtain a urethane unit. The end point of the reaction was confirmed by FT-IR by disappearance of the peak derived from the isocyanate group (around 2270 cm-1). Subsequently, as a reactive diluent, D.I. E. R. 331 (Product name, generic name: bisphenol A type epoxy resin, epoxy value 190, manufactured by Dow Chemical Co., Ltd.) 58.0 parts, 13.0 parts of glycidyl methacrylate as an ethylenically unsaturated monomer having an epoxy group, and others After adding 30.4 parts of n-butyl methacrylate as an ethylenically unsaturated monomer and stirring uniformly, the temperature is raised to 75 ° C. under a nitrogen atmosphere, where 2,2'-azobis (2,) as a polymerization initiator is used. 0.1 part of 4-dimethylvaleronitrile) was added in 13 portions every 30 minutes and reacted for another 2 hours after the addition of the polymerization initiator to form a (meth) acrylic unit. Then, the solvent was completely removed under reduced pressure to obtain a mixture of the urethane-acrylic composite resin (C-1) and the reactive diluent. The ratio (%) and number average molecular weight of the (meth) acrylic unit (B) in the obtained urethane-acrylic composite resin (C-1) are as shown in Table 1.

[Manufacturing Examples 2 to 16]
The same operation as in Production Example 1 was carried out except that the composition was changed to that shown in Table 1, to obtain a mixture of the urethane-acrylic composite resin (C-2 to 16) and the reactive diluent. The ratio (%) and number average molecular weight of the (meth) acrylic unit (B) in the obtained urethane-acrylic composite resin (C-2 to 16) are as shown in Table 1.

[Comparative Manufacturing Example 1]
100 parts of ADEKA polyether P-1000 (product name, generic name: bifunctional polypropylene glycol, hydroxyl value 110, manufactured by ADEKA) as a polyol in a reaction vessel equipped with a nitrogen gas introduction pipe, a stirrer, a thermometer, and a recirculator. , 28.3 parts of isophorone diisocyanate as an isocyanate group-containing compound and 0.02 parts of titanium diisopropoxybiz (ethylacetacetate) as a reaction accelerator were charged and uniformly stirred, and then reacted at 110 ° C. for 5 hours in a nitrogen atmosphere to make urethane. I got the resin. Subsequently, as a reactive diluent, D.I. E. R. Add 42.8 parts of 331 (product name, generic name: bisphenol A type epoxy resin, epoxy value 190, manufactured by Dow Chemical Co., Ltd.), mix well with stirring, and react with urethane resin (H-1) for comparison. A mixture with a sex diluent was obtained.

[Comparative Manufacturing Example 2]
In a reaction vessel equipped with a nitrogen gas introduction tube, a stirrer, a thermometer, and a reflux device, D.I. E. R. 331 (product name, generic name: bisphenol A type epoxy resin, epoxy value 190, manufactured by Dow Chemical Co., Ltd.) 4.8 parts, 4.3 parts of glycidyl methacrylate and 10.0 parts of n-butyl methacrylate were added and stirred uniformly. After that, the temperature was raised to 75 ° C. under a nitrogen atmosphere, and 0.1 part of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added thereto in 13 portions every 30 minutes. After adding all the polymerization initiators, the reaction was carried out for another 2 hours to obtain a mixture of a comparative acrylic resin (H-2) and a reactive diluent.

[Comparative Manufacturing Example 3]
The same operation as in Production Example 1 was carried out except that the composition was changed to that shown in Table 1, to obtain a mixture of a urethane-acrylic composite resin (H-3) for comparison and a reactive diluent. The ratio (%) and number average molecular weight of the (meth) acrylic unit (I) in the obtained urethane-acrylic composite resin (H-3) are as shown in Table 1.

[Comparative Manufacturing Example 4]
The same operation as in Production Example 1 was carried out except that a reactive diluent was not used, to obtain a urethane-acrylic composite resin (H-4) for comparison. The ratio (%) and number average molecular weight of the (meth) acrylic unit (B) in the obtained urethane-acrylic composite resin (H-4) are as shown in Table 1.

The compounds listed in Table 1 are shown below.
<Polyprethane>
-P-1000: Bifunctional polypropylene glycol, hydroxyl value 110, manufactured by ADEKA-P-2000: Bifunctional polypropylene glycol, hydroxyl value 56, manufactured by ADEKA-PEG1000: Bifunctional polyethylene glycol, hydroxyl value 112.2, Nichiyu <Isocyanate group-containing compound>
-IPDI: Isophorone diisocyanate <Reactive diluent (E)>
D. E. R. 331: Bisphenol A type epoxy resin, epoxy value 190, manufactured by Dow Chemical Co., Ltd. <Ethylene unsaturated monomer>
-BMA: n-butyl methacrylate-MMA: methyl methacrylate <Epoxy unsaturated monomer (G)>
-GMA: glycidyl methacrylate-4HBAGE: 4-hydroxybutyl acrylate glycidyl ether

<Preparation of adhesive resin composition>
[Example 1]
10 parts of mixture of urethane / acrylic composite resin (C-1) and reactive diluent, 0.36 parts of dicyandiamide as curing agent (D), N, N-dimethyl-N'-(4-chlorophenyl) as curing accelerator ) 0.05 part of urea was stirred and mixed at room temperature to prepare the adhesive resin composition of Example 1.

[Examples 2 to 16 and Comparative Examples 1 to 6]
The same operations as in Example 1 were carried out except that the composition was changed to the composition shown in Table 2, and the adhesive resin compositions of Examples 2 to 16 and Comparative Examples 1 to 6 were prepared. In Comparative Example 2, the following evaluation test was not carried out because the viscosity was high and it was difficult to uniformly stir and mix.

<Evaluation of adhesive resin composition>
The following tests were carried out on the adhesive resin compositions prepared in Examples 1 to 16 and Comparative Examples 1 and 3 to 6. The determination results are shown in Table 2.

[Adhesive strength]
Each adhesive composition is applied onto an aluminum base material (length 100 mm, width 25 mm, film thickness 2 mm) so as to have a width of 25 mm, a length of 10 mm, and a thickness of 0.1 mm, and a carbon fiber reinforced plastic substrate (length 100 mm). , Width 25 mm, film thickness 2 mm) and cured at 160 ° C. for 1 hour in a state of being pressure-bonded to maintain a thickness of 0.1 mm to obtain a test piece for adhesive strength evaluation. The obtained test piece was measured for shear adhesion strength using a tensile tester at a tensile speed of 1 mm / min under the conditions of a temperature of 25 ° C. and a relative humidity of 50%, and was judged according to the following evaluation criteria. The practical level is △ or higher.
(Evaluation criteria)
◯: 15 MPa or more.
◯ Δ: 12.5 MPa or more and less than 15 MPa.
Δ: 10 MPa or more and less than 12.5 MPa.
X: Less than 10 MPa.

[Fracture elongation (flexibility)]
Each curable composition was filled in a sheet-shaped mold having a thickness of 3 mm, the surface was prepared, cured at 160 ° C. for 1 hour, and then punched with a dumbbell mold to prepare a dumbbell-shaped cured product. Using this dumbbell piece, a tensile test was conducted at a tensile speed of 50 mm / min, the elongation rate (%) at break was measured, and the judgment was made according to the following criteria. The practical level is △ or higher.
(Evaluation criteria)
◯: 20% or more.
◯ Δ: 10% or more and less than 20%.
Δ: 5% or more and less than 10%.
X: Less than 5%.

From Table 2, the adhesive resin composition of the present invention gave good results in both adhesive strength and elongation at break (flexibility). On the other hand, in the comparative adhesive resin composition, the adhesive strength and / or the elongation at break (flexibility) were inferior to those in the examples.

[Manufacturing Examples 17 to 34]
The same operation as in Production Example 1 was carried out except that the composition was changed to that shown in Table 3, to obtain a mixture of urethane-acrylic composite resin (C-17 to 34) and a reactive diluent. Table 3 shows the ratio (%) of the (meth) acrylic unit (B) in the obtained urethane-acrylic composite resin (C-17 to 34), the number average molecular weight, and the like.

[Comparative Manufacturing Example 5]
The same operation as in Production Example 1 was carried out except that the composition was changed to that shown in Table 3, and a mixture of a urethane-acrylic composite resin (H-5) for comparison and a reactive diluent was obtained. Table 3 shows the ratio (%) of the (meth) acrylic unit (I) in the obtained urethane-acrylic composite resin (H-5), the number average molecular weight, and the like.

[Comparative Manufacturing Example 6]
The same operation as in Production Example 1 was carried out except that a reactive diluent was not used, to obtain a urethane-acrylic composite resin (H-6) for comparison. Table 3 shows the ratio (%) and number average molecular weight of the (meth) acrylic unit (B) in the obtained urethane-acrylic composite resin (H-6).

The compounds listed in Table 3 are listed below.
<Polyprethane>
HF-2009: Bifunctional castor oil-based polyol, hydroxyl value 43.2, manufactured by Ito Oil Co., Ltd., trade name "URIC HF-2009"
<Isocyanate group-containing compound>
-MDI: Diphenylmethane diisocyanate socyanate

[Examples 17 to 34 and Comparative Examples 7 and 8]
The same operations as in Example 1 were carried out except that the composition was changed to the composition shown in Table 4, and the adhesive resin compositions of Examples 17 to 34 and 7 and 8 were prepared.

[Adhesive strength]
Each adhesive composition is applied onto an aluminum base material (length 100 mm, width 25 mm, film thickness 2 mm) so as to have a width of 25 mm, a length of 10 mm, and a thickness of 0.1 mm, and a carbon fiber reinforced plastic substrate (length 100 mm, length 100 mm, A test piece for evaluation of adhesive strength was obtained by laminating with a width of 25 mm and a film thickness of 2 mm) and curing at 160 ° C. for 1 hour in a state of being pressure-bonded to maintain a thickness of 0.1 mm. The obtained test piece was measured for shear adhesive strength at a tensile speed under the same conditions as described above, and was judged by the above adhesive strength evaluation criteria. The practical level is 10 MPa or more, and the larger the value, the better.

[Fracture elongation (flexibility)]
Each curable composition was filled in a sheet-shaped mold having a thickness of 3 mm, the surface was prepared, cured under the same curing conditions as described above, and then punched with a dumbbell mold to prepare a dumbbell-shaped cured product. This dumbbell piece was measured in the same manner as described above, and was judged according to the above criteria. The practical level is 10% or more, and the larger the value, the better.

[Examples 35-68, Comparative Examples 9-12]
The same operations as in Example 1 were carried out except that the composition was changed to the composition shown in Table 5, and the adhesive resin compositions of Examples 35 to 68 and Comparative Examples 9 to 12 were prepared.

[Heat-resistant]
Each curable composition was filled in a sheet-shaped mold having a thickness of 1 mm, the surface was prepared, and the mixture was cured at 160 ° C. for 1 hour. A strip-shaped sample cured film for dynamic viscoelasticity measurement was cut into strips having a width of 5 mm to obtain test pieces, which were allowed to stand in an oven at 150 ° C. for 500 hours. Dynamic viscoelasticity measurements were performed on the test pieces before and after the heat resistance test using DVA-200 / L2 (IT Measurement Control Co., Ltd.). The measurement conditions are as follows.

Measurement mode: Tension mode Frequency: 10Hz
Temperature range: -80 ° C to measurement limit Heating conditions: 10 ° C / min

Using the value of the storage elastic modulus at 200 ° C., the rate of change was calculated by the following formula. The closer the value is to zero, the better. When the storage elastic modulus of the test piece before the heat resistance test at 200 ° C. is A (Pa) and the storage elastic modulus of the test piece after the heat resistance test at 200 ° C. is B (Pa), the rate of change C is as follows. Represented in.
(1) When A> B: C = A / B
(2) When B ≧ A: C = B / A

(Evaluation criteria)
〇: C is less than 10 Δ: C is 10 or more and less than 100 ×: C is 100 or more

From Tables 4 and 5, the adhesive resin composition of the present invention gave good results in heat resistance. On the other hand, the heat resistance of the comparative adhesive resin composition was inferior to that of the examples.

Claims (5)

Contains a urethane-acrylic composite resin (C), a curing agent (D), and a reactive diluent (E) in which a urethane unit (A) and a (meth) acrylic unit (B) are linked by a residue of a chain transfer agent. The adhesive resin composition (F) to be used, wherein the (meth) acrylic unit (B) has a structural unit derived from an ethylenically unsaturated monomer (G) having an epoxy group. Composition (F). The adhesive resin composition (F) according to claim 1, wherein the urethane unit (A) and the (meth) acrylic unit (B) are linked by a residue of a chain transfer agent having an amino group. ). The claim is characterized in that the content of the structural unit derived from the ethylenically unsaturated monomer (G) having an epoxy group is 5 to 100 parts by weight out of 100 parts by weight of the (meth) acrylic unit (B). Item 2. The adhesive resin composition (F) according to Item 1 or 2. The invention according to any one of claims 1 to 3, wherein the content of the (meth) acrylic unit (B) is 10 to 60 parts by weight out of 100 parts by weight of the urethane / acrylic composite resin (C). Adhesive resin composition (F). A laminate obtained by forming an adhesive layer on a base material using the resin composition (F) according to any one of claims 1 to 4.