JP7447484B2 - Resin composition and laminate - Google Patents

Description

The present invention relates to a resin composition that can be used for film base materials, adhesives, coating agents, elastomers, etc. in the fields of medical materials and optical materials.

Examples of resins suitably used in industrial applications include acrylic resins, which can be designed in a wide variety of ways to suit the application due to the wide selection of raw materials, and urethane resins, which can provide wear resistance and flexibility. Furthermore, by introducing a crosslinkable functional group into these resins, the crosslinking density of the cured product can be increased and the strength can be improved. Therefore, acrylic resins and urethane resins are being studied in a wide range of fields such as film base materials, adhesives, coating agents, and elastomers.

However, in general, acrylic resin alone can provide coatings or molded products with relatively high strength, but the problem is that it lacks extensibility and stress relaxation properties, while urethane resin alone has poor extensibility. However, when designed to provide strength, the problem is that the extensibility is lost, and it has been difficult to achieve both strength and extensibility.

To address the above issues, for example, in Patent Document 1, an acrylic resin is polymerized in the presence of a urethane resin to form a composite film consisting of a urethane resin and an acrylic resin. sheet is proposed. However, since acrylic resins and urethane resins generally have poor compatibility and the range of application is limited, it has not been possible to achieve both coating film strength and extensibility for applications that require higher strength.

Japanese Patent Application Publication No. 2012-1726

An object of the present invention is to provide a resin composition having excellent coating film strength and high elongation and flexibility, and a laminate using the resin composition.

As a result of intensive studies to solve the above problems, it was discovered that the above problems could be solved by the embodiments shown below, and the present invention was completed.

An embodiment of the present invention contains a urethane-acrylic composite resin (C) in which a urethane unit (A) and a (meth)acryloyl unit (B) are connected via a chain transfer agent residue, and a polymerizable compound (D). A resin composition,
The present invention relates to a resin composition in which the (meth)acryloyl unit (B) includes a structural unit having an ethylenically unsaturated double bond.

Another embodiment of the present invention relates to the resin composition, wherein the urethane unit (A) and the (meth)acryloyl unit (B) are linked by a residue of a chain transfer agent having an amino group.

Another embodiment of the present invention is the resin composition, wherein the content of the structural unit having an ethylenically unsaturated double bond is 20 to 85 parts by mass in 100 parts by mass of the (meth)acryloyl unit (B). Regarding.

Another embodiment of the present invention relates to the resin composition, wherein the content of the urethane unit (A) is 45 to 90 parts by mass in 100 parts by mass of the urethane-acrylic composite resin (C).

Another embodiment of the present invention relates to the resin composition, wherein the urethane-acrylic composite resin (C) has a number average molecular weight of 8,000 to 50,000.

Another embodiment of the present invention relates to a laminate including a resin layer formed from the resin composition above on a base material.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which has excellent coating film strength and high extensibility and flexibility, and the laminated body formed using this resin composition can be provided.

The resin composition of the present invention contains a urethane-acrylic composite resin (C) in which a urethane unit (A) and a (meth)acryloyl unit (B) are connected by a chain transfer agent residue, and a polymerizable compound (D). The (meth)acryloyl unit (B) is characterized in that it contains a structural unit having an ethylenically unsaturated double bond. The resin composition of the present invention is useful in fields such as film base materials, adhesives, coating agents, elastomers, medical materials, and optical materials.
The present invention will be explained in detail below.

<Urethane/acrylic composite resin (C)>
The urethane-acrylic composite resin (C) of the present invention has a structure in which a urethane unit (A) and a (meth)acryloyl unit (B) are connected by a chain transfer agent residue, and the (meth)acryloyl unit It is sufficient that (B) contains a structural unit having an ethylenically unsaturated double bond, and the manufacturing method thereof is not limited, but preferably, for example, it can be manufactured by the following method.

First, a urethane unit (A) having isocyanate groups at both ends, which is obtained by reacting a polyol and a polyisocyanate, is formed (hereinafter, step 1).
Next, a chain transfer agent is added to synthesize a urethane prepolymer having chain transfer agent residues at both ends of the urethane unit (A) (hereinafter, step 2).
Thereafter, using the chain transfer agent residue of the obtained urethane prepolymer, an ethylenically unsaturated monomer containing a (meth)acrylic monomer (b1) having a reactive group is transferred in the presence of a polymerization initiator. chain transfer polymerization to form a (meth)acryloyl unit having a reactive group in the side chain (hereinafter, step 3).
Next, the reactive group of the side chain is reacted with an ethylenically unsaturated compound (b2) having a group capable of reacting with the reactive group in the molecule to form a structural unit having an ethylenically unsaturated double bond. A (meth)acryloyl unit (B) containing (hereinafter, step 4) is formed.

In this way, the urethane-acrylic composite resin (C ) can be obtained. All of these reactions may be carried out using a solvent or without using a solvent. Furthermore, when a solvent is used, the solvent may be removed during the reaction or after the reaction is completed under reduced pressure or normal pressure.

<Urethane unit (A)>
The urethane-acrylic composite resin (C) in the present invention has a structure in which a urethane unit (A) and a (meth)acryloyl unit (B) are connected by a chain transfer agent residue, and the urethane unit ( A) can be formed by reacting a polyol and a polyisocyanate.

<Polyol>
Examples of the polyol constituting the urethane unit include polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, vegetable oil polyol, and other polyols. These may be used alone or in combination of two or more.

(Polyether polyol)
Examples of polyether polyols include polymers or copolymers of methylene oxide, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, etc., such as polyethylene glycol, polypropylene glycol, poly(ethylene/propylene) glycol, polytetramethylene glycol, etc. glycols; hexanediol, methylhexanediol, heptanediol, octanediol, or condensates of mixtures thereof; compounds with two or more active hydrogen groups include methylene oxide, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, or a polyol obtained by adding an alkylene oxide such as polyoxytetramethylene oxide; and the like.

Examples of the compound having two or more active hydrogen groups include low-molecular polyols, aliphatic amine compounds, aromatic amine compounds, alkanolamines, and bisphenols.

Examples of the low molecular polyol include bifunctional low molecular polyols, trifunctional or higher functional low molecular polyols, and the like.

The difunctional low-molecular polyol is not particularly limited and includes, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4 -Butanediol, neopentyl glycol, pentanediol, 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 (number of added moles: 10 or less), polyoxypropylene glycol (number of added moles: 10 or less) ), cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadienedimethanol, dimer diol, bisphenol A, N,N-bis(2-hydroxypropyl)aniline, dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutane Examples include 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, dihydroxysuccinic acid, dihydroxypropionic acid, and dihydroxybenzoic acid.

The trifunctional or higher-functional low-molecular polyol is not particularly limited and includes, for example, trimethylolethane, trimethylolpropane, 1,1,1-trimethylolbutane, 1,2,3-butanetriol, 1,2,4- Butanetriol, 1,2,6-butanetriol, trimethylolbutene, trimethylolpentene, trimethylolhexene, trimethylolheptene, trimethyloloctene, trimethylolnonene, trimethyloldecene, trimethylolundecene, trimethyloldodecene , trimethyloltridecene, trimethylolpentadecene, trimethylolhexadecene, trimetrolheptadecene, 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-trimethyloldecane, 1,2,10-decanetriol, 1, 1,1-trimethylol isoheptadecane, 1,1,1-trimethylol-sec-butane, 1,1,1-trimethylol-tert-pentane, 1,1,1-trimethylol-tert-nonane, 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-butanetetraol, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin, triglycerin, polyglycerin, ditrimethylolethane, ditrimethylolpropane, tris(2-hydroxyethyl)isocyanurate, benzene -1,3,5-triol, benzene-1,2,3-triol, stilbene-3,4',5-triol, sucrose, inositol, sorbitan, sorbitol, mannitol, sucrose, cellulose, and xylitol.

Examples of aliphatic amine compounds include ethylenediamine, triethylenetetramine, diethylenetriamine, and triaminopropane. Examples of aromatic amine compounds include toluenediamine and diphenylmethane-4,4-diamine. Examples of alkanolamines include ethanolamine and diethanolamine. Examples of bisphenols include bisphenol A, bisphenol AP, bisphenol B, bisphenol C, bisphenol E, and bisphenol F.

(Polyester polyol)
Examples of the polyester polyol include polyester polyols obtained by a condensation reaction between the above-mentioned low-molecular-weight polyol and a dibasic acid component.
Dibasic acid components include terephthalic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, hydrogenated dimer acid, phthalic anhydride, isophthalic acid, trimellitic acid, glutaric acid, pimelic acid, suberic acid, sebacic acid, etc. aliphatic or aromatic dibasic acids, and anhydrides thereof.

Further, as the polyester polyol, a polyester polyol obtained by ring-opening polymerization of a lactone cyclic ester compound such as ε-caprolactone, poly(β-methyl-γ-valerolactone), and polyvalerolactone may be used.

(Polycarbonate polyol)
Examples of polycarbonate polyols include those obtained by reacting the above-mentioned low-molecular-weight polyols with carbonate compounds such as dialkyl carbonates, alkylene carbonates, and diaryl carbonates.
Dimethyl carbonate or diethyl carbonate can be used as the dialkyl carbonate, ethylene carbonate or the like can be used as the alkylene carbonate, and diphenyl carbonate can be used as the diaryl carbonate.

(Polyolefin polyol)
Examples of the polyolefin 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.

(vegetable oil polyol)
Examples of the vegetable oil-based polyol include polyols made from plant-derived castor oil, dimer acid, or soybean oil.

The polyol is preferably a polyether polyol, a polyester polyol, a polyolefin polyol or a polycarbonate polyol, and more preferably a polyether polyol or a polyolefin polyol.

The number average molecular weight of the polyol is preferably 500 or more and less than 5,000, more preferably 700 or more and less than 3,500.

The polyol may contain polyols other than those mentioned above, and the above-mentioned low-molecular-weight polyols can be used in combination for the purpose of adjusting the urethane bond concentration and introducing various functional groups.

<Polyisocyanate>
Examples of the polyisocyanate constituting the urethane unit (A) include aromatic, aliphatic, or alicyclic diisocyanates. These may be used alone or in combination of two or more.

Examples of aromatic diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, , 2'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, toridine diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, p-tetramethylxylene diisocyanate, 3,3'-dimethyl-4 , 4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, and 1,5-tetrahydronaphthalene diisocyanate.

Examples of aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2 , 4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, trimethylhexamethylene Diisocyanates are mentioned.

Examples of the alicyclic diisocyanate include isophorone diisocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane. Examples include diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, hydrogenated xylylene diisocyanate, dimer acid diisocyanate, and norbornene diisocyanate.

The reaction between a polyol and a polyisocyanate can be preferably carried out without a solvent using a known urethanization reaction, and by using an excess of polyisocyanate, a urethane unit having isocyanate groups at both ends can be obtained. can. The molar ratio of isocyanate groups to hydroxyl groups (number of NCO moles/number of OH moles) during the reaction is preferably 1.05 to 2.00, more preferably 1.10 to 1.50.
In the urethanization reaction, a catalyst may be used for the purpose of adjusting reactivity.

(catalyst)
As the catalyst, known metal catalysts, amine catalysts, etc. can be used. Examples of metal catalysts include dibutyltin dilaurate, tin octoate, dibutyltin di(2-ethylhexoate), lead 2-ethylhexoate, 2-ethylhexyl titanate, titanium ethyl acetate, and 2-ethylhexoate. Examples include iron, cobalt 2-ethylhexoate, zinc naphthenate, cobalt naphthenate, and tetra-n-butyltin. Examples of the amine catalyst include tertiary amines such as tetramethylbutanediamine. The amount of catalyst used is preferably in the range of 0.05 to 1 mol% based on the polyol.

(Content of urethane unit (A))
The content of the urethane unit (A) is preferably 25 to 90 parts by mass, more preferably 45 to 90 parts by mass, and even more preferably 60 to 85 parts by mass in 100 parts by mass of the urethane/acrylic composite resin (C). Part by mass. It is preferable to include 25 to 90 parts by mass of the urethane unit (A) because the resin layer formed from the resin composition has excellent extensibility, scratch resistance, adhesive strength, and flexibility.

<Chain transfer agent>
By reacting the urethane unit (A) obtained above and a chain transfer agent, a urethane prepolymer having chain transfer agent residues at both ends can be obtained.
The chain transfer agent is not particularly limited, but one preferably has a functional group capable of reacting with an isocyanate group and a sulfanyl group. When the chain transfer agent is used, the terminal isocyanate group in the urethane unit (A) and the functional group that can react with the isocyanate group in the chain transfer agent react, and a urethane prepolymer having sulfanyl groups at both ends is formed. .
The chain transfer agent can be used alone or in combination of two or more known chain transfer agents.

Examples of the functional group that can react with the isocyanate group include a hydroxyl group and an amino group, and from the viewpoint of reactivity, an amino group is preferable. Amino groups have higher reactivity than sulfanyl groups, so they preferentially react with the terminal isocyanate groups of urethane units to form urea bonds, making it possible to efficiently introduce sulfanyl groups at the terminals of urethane prepolymers. preferable.

Examples of compounds having one amino group and one sulfanyl group in the molecule include 2-aminoethanethiol, 3-aminopropyl-1-thiol, 1-aminopropyl-2-thiol, and 4-amino-1-thiol. Examples include aminoalkanethiols such as butanethiol; aminobenzenethiols such as 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Among these, aminoalkanethiols are preferred, and 2-aminoethanethiol is more preferred.

<(Meta)acryloyl unit (B)>
The (meth)acryloyl unit (B) contains a structural unit having an ethylenically unsaturated double bond, and specifically, the urethane precipitate obtained in step 2 and having chain transfer agent residues at both ends. A polymer and an ethylenically unsaturated monomer containing a (meth)acrylic monomer (b1) having a reactive group are polymerized in the presence of a polymerization initiator to form a polymer having a reactive group in its side chain ( After forming the meth)acryloyl unit, the urethane unit (A) and ( A urethane having a structure in which the meth)acryloyl unit (B) is connected by a chain transfer agent residue, and the (meth)acryloyl unit (B) contains a constituent unit having an ethylenically unsaturated double bond. - Acrylic composite resin (C) can be obtained.

<(meth)acrylic monomer (b1) having a reactive group>
The reactive group of the (meth)acrylic monomer (b1) having a reactive group is preferably at least one group selected from the group consisting of a hydroxyl group, an isocyanate group, a carboxyl group, and an epoxy group. The carboxyl group may form an acid ring. These may be used alone or in combination of two or more.

Examples of the (meth)acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. , 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate or these Caprolactone adduct of monomer (number of moles added is 1 to 5), polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, glycerin mono(meth)acrylate, N-(2-hydroxyethyl)(meth)acrylamide, N -methylol(meth)acrylamide, N,N-di(methylol)acrylamide, and N-methylol-N-methoxymethyl(meth)acrylamide.

Examples of the (meth)acrylic monomer having an isocyanate group include 2-isocyanatoethyl (meth)acrylate, 4-isocyanatobutyl methacrylate, 4-isocyanatobutyl (meth)acrylate, and 1,1-(bisacryloyloxy). Examples include methyl)ethyl isocyanate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, (meth)acryloyloxyethoxyethyl isocyanate, (meth)acryloyloxyethoxyethyl isocyanate, and (meth)acryloyloxypropylisocyanate.
Further, as the (meth)acrylic monomer having an isocyanate group, a product obtained by reacting a hydroxyl group in the above-mentioned hydroxyl group-having (meth)acrylic monomer with a polyisocyanate may be used. As the polyisocyanate, the polyisocyanate described in the section of the urethane unit (A) above can be used.

Examples of (meth)acrylic monomers having a carboxyl group include (meth)acrylic acid, itaconic acid, 2-(meth)acryloyloxyethylsuccinic acid, and 2-(meth)acryloyloxyethyl phthalic acid. , 2-(meth)acryloyloxyhexahydrophthalic acid and the like are compounds obtained by reacting a (meth)acrylic monomer having a hydroxyl group with an acid anhydride. Examples of the acid anhydride include trimellitic anhydride, succinic anhydride, maleic anhydride, fumaric anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, glutaric anhydride, and adipic anhydride. , succinic anhydride, itaconic anhydride, butane-1,2,3,4-tetracarboxylic dianhydride.
Furthermore, examples of the compounds in which the carboxyl group forms an anhydride ring include maleic anhydride and itaconic anhydride.

Examples of the (meth)acrylic monomer having an epoxy group include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, ( Examples include 6,7-epoxypentyl meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and lactone-modified 3,4-epoxycyclohexyl (meth)acrylate.

(Ethylenically unsaturated monomer)
The ethylenically unsaturated monomer used in step 3 is not particularly limited as long as it is copolymerizable with the (meth)acrylic monomer (b1) having a reactive group, and may be selected from known monomers. It can be selected as appropriate.
Examples of ethylenically unsaturated monomers other than the (meth)acrylic monomer (b1) having a reactive group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. ) acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-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 Linear or branched alkyl ethylenically unsaturated monomers such as; cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate , cyclic alkyl (meth)acrylates such as dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and isobornyl (meth)acrylate; trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, Fluoroalkyl ethylenically unsaturated monomers such as perfluorooctylethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate, 3-methyl-3-oxetanyl (meth)acrylate, etc. Ethylenically unsaturated monomers having a heterocycle; benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, paracumylphenoxyethyl (meth)acrylate, paracumylphenoxypolyethylene glycol (meth)acrylate, ) acrylate, or (meth)acrylates having an aromatic ring such as nonylphenoxypolyethylene glycol (meth)acrylate; 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, phenoxypolyethylene glycol polypropylene glycol mono(meth)acrylate, polyethylene glycol monomethyl ether(meth)acrylate, lauroxypolyethylene glycol mono (meth)acrylate, nonylphenoxypolyethylene glycol mono(meth)acrylate, nonylphenoxypolypropylene glycol mono(meth)acrylate, nonylphenoxypolyethylene glycol polypropylene glycol mono(meth)acrylate, phenoxypolyethylene glycol mono(meth)acrylate, methoxypolyethylene glycol ( Ethylenically unsaturated with an alkyl ether group such as meth)acrylate, n-butoxyethyl(meth)acrylate, n-butoxydiethylene glycol(meth)acrylate, 2-methoxyethyl(meth)acrylate, 2-ethoxyethyl(meth)acrylate, etc. Monomers: 3-(acryloyloxymethyl)3-methyloxetane, 3-(methacryloyloxymethyl)3-methyloxetane, 3-(acryloyloxymethyl)3-ethyloxetane, 3-(methacryloyloxymethyl)3- Ethyloxetane, 3-(acryloyloxymethyl)3-butyloxetane, 3-(methacryloyloxymethyl)3-butyloxetane, 3-(acryloyloxymethyl)3-hexyloxetane and 3-(methacryloyloxymethyl)3-hexyloxetane ethylenically unsaturated monomers having an oxetanyl group such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth)acrylate, or allyl (meth)acrylate; Ethylenically 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; aminoethyl (meth)acrylate, dimethylaminoethyl (meth) ) acrylate, diethylaminoethyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, dipropylaminoethyl (meth)acrylate, t-butylaminoethyl methacrylate, methylethylaminoethyl (meth)acrylate, N-aminoethyl (meth)acrylate 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 and their salts; cyano group-containing ethylenically unsaturated monomers such as (meth)acrylonitrile, cyanostyrene, cyanoacrylate, nitrostyrene, etc. (meth)acrylamide, N-methyl (meth)acrylamide, N-butylacrylamide, 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-vinyl Acetamide, N-vinylpyrrolidone, N,N-di(methoxymethyl)acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N,N-di(ethoxymethyl)acrylamide, N-ethoxymethyl-N-propoxymethyl Methacrylamide, N,N-di(propoxymethyl)acrylamide, N-butoxymethyl-N-(propoxymethyl)methacrylamide, N,N-di(butoxymethyl)acrylamide, N-butoxymethyl-N-(methoxymethyl) Amide group-containing ethylenically unsaturated monomers such as methacrylamide, N,N-di(pentoxymethyl)acrylamide, N-methoxymethyl-N-(pentoxymethyl)methacrylamide, and cinnamic acid amide; trimethylammonioethyl (meth)acrylate chloride, methyldiethylammonioethyl (meth)acrylate bromide, trimethylammonioethyl (meth)acrylamide methosulfate, benzyldiethylammonioethyl (meth)acrylamide carbonate, dimethyldiallylammonium chloride, trimethylallylammonium chloride, etc. Ethylenically unsaturated monomers containing quaternary ammonium cations; acrolein, N-vinylformamide, formylstyrene, (meth)acrylamidopivalaldehyde, butanediol-1,4-acrylate-acetylacetate, acrylamidemethylanisaldehyde, etc. Ethylenically unsaturated monomers containing aldehyde groups; diacetone (meth)acrylamide, N-vinylacetamide, vinyl methyl ketone, vinyl ethyl ketone, acetoxyethyl (meth)acrylate, cyanoacetoxyethyl (meth)acrylate, N- (cyanoacetoxyethyl)acrylamide, N-(propionylacetoxybutyl)acrylamide, N-(4-acetoacetoxymethylbenzyl)acrylamide, N-(2-acetoacetylaminoethyl)acrylamide, etc. mer; acetoacetoxymethyl (meth)acrylate, acetoacetoxyethyl (meth)acrylate, acetoacetoxypropyl (meth)acrylate, acetoacetoxybutyl (meth)acrylate, 2-acetoacetoxy-1-methylethyl (meth)acrylate, 2 Ethylenically unsaturated monomers having a β-diketone structure such as -ethoxymalonyloxyethyl (meth)acrylate;
These may be used alone or in combination of two or more.

<Ethylenically unsaturated compound (b2) having a group capable of reacting with a reactive group in the molecule>
The group capable of reacting with the reactive group in the ethylenically unsaturated compound (b2) is preferably at least one group selected from the group consisting of a hydroxyl group, an isocyanate group, a carboxyl group, and an epoxy group, Those listed for the meth)acrylic monomer (b1) can be used.
Further, as the ethylenically unsaturated compound (b2), a compound having one hydroxyl group and two or more (meth)acryloyl groups in the molecule may be used. Examples of compounds having one hydroxyl group and two or more (meth)acryloyl groups in the molecule include trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, Examples include isocyanuric acid EO-modified di(meth)acrylate. These may be used alone or in combination of two or more.

The combination of the reactive group in the (meth)acrylic monomer (b1) having a reactive group and the group capable of reacting with the reactive group in the ethylenically unsaturated compound (b2) is preferably (i) hydroxyl group and isocyanate group, (ii) carboxyl group and epoxy group, or (iii) carboxylic anhydride and hydroxyl group, more preferably (i) hydroxyl group and isocyanate group, or (ii) carboxyl group and epoxy group. It's a combination.
As for (i), an ethylenically unsaturated monomer having an isocyanate group is added to the side chain hydroxyl group of a (meth)acryloyl unit obtained by polymerizing an ethylenically unsaturated monomer containing a (meth)acrylic monomer having a hydroxyl group. The isocyanate group of a saturated monomer may be reacted, or the side of a (meth)acryloyl unit obtained by copolymerizing an ethylenically unsaturated monomer containing a (meth)acrylic monomer having an isocyanate group. The isocyanate group of the chain may be reacted with the hydroxyl group of an ethylenically unsaturated monomer having a hydroxyl group.
As for (ii), ethylene having an epoxy group is added to the side chain carboxyl group of a (meth)acryloyl unit obtained by polymerizing an ethylenically unsaturated monomer containing a (meth)acrylic monomer having a carboxyl group. The side of the (meth)acryloyl unit obtained by reacting the epoxy group of the ethylenically unsaturated monomer, or by polymerizing the ethylenically unsaturated monomer containing the (meth)acrylic monomer having an epoxy group. The epoxy group of the chain may be reacted with the carboxyl group of an ethylenically unsaturated monomer having a carboxyl group.

The content of the structural unit having an ethylenically unsaturated double bond is preferably 5 to 100 parts by mass, more preferably 15 to 90 parts by mass, and even more preferably 20 parts by mass in 100 parts by mass of the (meth)acryloyl unit (B). ~85 parts by mass. A content of 5 to 100 parts by mass is preferable because the resin layer formed from the resin composition of the present invention has excellent extensibility, scratch resistance, adhesive strength, and flexibility.
The content of the structural unit having an ethylenically unsaturated double bond is the (meth)acrylic monomer (b1) having a reactive group and the ethylenically unsaturated unit having a group capable of reacting with the above reactive group in the molecule. It can be calculated by dividing the sum of compound (b2) by the total number of (meth)acryloyl units.

<Polymerization initiator>
As the polymerization initiator, known azo compounds and organic peroxides can be used. These may be used alone or in combination of two or more.
The azo compound is not particularly limited and includes, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane 1- 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].
The organic peroxide is not particularly limited, and examples thereof include benzoyl peroxide, t-butyl peroxy 2-ethyl hexaate, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n -propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl)peroxide, Examples include dipropionyl peroxide and diacetyl peroxide.

The amount of the polymerization initiator used is preferably 0.001 to 15 parts by weight based on 100 parts by weight of all ethylenically unsaturated monomers. A range of 0.001 to 15 parts by mass is preferable because chain transfer polymerization proceeds effectively.

(Number average molecular weight of urethane/acrylic composite resin (C))
The number average molecular weight of the urethane-acrylic composite resin (C) is preferably 7,000 to 100,000, more preferably 8,000 to 60,000, and even more preferably 8,000 to 50,000. It is. A value of 7,000 to 100,000 is preferable because the resin layer formed from the resin composition has excellent extensibility, scratch resistance, adhesive strength, and flexibility.

(Double bond equivalent of urethane/acrylic composite resin (C))
The double bond equivalent of the urethane-acrylic composite resin (C) is preferably 200 to 5,000, more preferably 300 to 3,000, and even more preferably 350 to 2,000. The double bond equivalent is expressed as (mass of resin having double bonds (g))/(number of double bonds contained in resin having double bonds (mol)), and is calculated by the following formula. Ru.
Double bond equivalent = (total mass (g) of urethane-acrylic composite resin (C)) / (amount of ethylenically unsaturated double bonds derived from structural units having ethylenically unsaturated double bonds (mol))

<Solvent>
Produce urethane-acrylic composite resin (C) through reactions between polyols and polyisocyanates, reactions between urethane units and chain transfer agents, and reactions in which (meth)acrylic monomers are polymerized using chain transfer agent residues. The reaction may be carried out using a solvent. Examples of solvents that may be used include ethers such as dibutyl ether, dimethoxymethane, dimethoxyethane, propylene oxide, 1,3-dioxolane, 1,4-dioxane, and tetrahydrofuran; methyl acetate, ethyl acetate, propyl acetate, and acetic acid. Esters such as butyl; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; as well as toluene, xylene, methylcyclohexane, acetonitrile, methoxypropyl acetate, and diethoxydiethylene glycol. One type of solvent may be used alone, or two or more types may be used in combination.

<Polymerizable compound (D)>
The resin composition of the present invention further contains a polymerizable compound (D).
As the polymerizable compound (D), photopolymerizable monomers or photopolymerizable oligomers having the property of being cured by active energy rays such as ultraviolet rays or electron beams can be used, and these may be used alone. Alternatively, two or more types may be used in combination.

Examples of photopolymerizable oligomers include epoxy (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, and acrylic (meth)acrylate, which can be used singly. They may be used, or two or more types may be used in combination.

Epoxy (meth)acrylate oligomers can be produced by, for example, reacting and esterifying the oxirane ring of a relatively low molecular weight bisphenol-type epoxy resin or novolac-type epoxy resin with the above-mentioned (meth)acrylic monomer having a carboxyl group. It can be obtained by Furthermore, a carboxyl-modified epoxy (meth)acrylate oligomer obtained by partially modifying this epoxy (meth)acrylate oligomer with a dibasic carboxylic anhydride may be used.

The urethane (meth)acrylate oligomer is, for example, an isocyanate group obtained by reacting the above-mentioned polyisocyanate, a compound having a trifunctional or more functional isocyanate group, and the above-mentioned polyol with the above-mentioned polyisocyanate under conditions in which there is an excess of isocyanate groups. One or more compounds selected from the group consisting of containing urethanes, the above-mentioned (meth)acrylic monomer having a hydroxyl group, and a compound having one hydroxyl group and two or more (meth)acryloyl groups in the molecule. It can be obtained by reacting at least one compound selected from the group consisting of: Further, a hydroxyl group-containing urethane obtained by reacting the above-mentioned polyol and the above-mentioned polyisocyanate under conditions with an excess of hydroxyl groups, the above-mentioned polyol, and the above-mentioned hydroxyl group-containing (meth)acrylic monomer group selected from the group consisting of It can be obtained by reacting at least one compound and the above-mentioned (meth)acrylic monomer having an isocyanate group.

A polyester (meth)acrylate oligomer is, for example, a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyhydric carboxylic acid and a polyhydric alcohol, and a (meth)acrylic monomer having a carboxyl group as described above. It can be obtained by esterification with. Further, it can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid with the above-mentioned (meth)acrylic monomer having a carboxyl group. In addition, the carboxyl groups of a polyester oligomer having carboxyl groups at both ends obtained by condensation of a polyhydric carboxylic acid and a polyhydric alcohol can be replaced with the above-mentioned (meth)acrylic monomer having a hydroxyl group and one hydroxyl group in the molecule. It can be obtained by esterification with at least one compound selected from the group consisting of compounds having two or more (meth)acryloyl groups.

The polyether (meth)acrylate oligomer can be obtained, for example, by esterifying the hydroxyl group of a polyether polyol with the above-mentioned (meth)acrylic monomer having a carboxyl group.

In addition, photopolymerizable oligomers include highly hydrophobic polybutadiene (meth)acrylate oligomers that have (meth)acrylate groups in their side chains, and silicone (meth)acrylate oligomers that have polysiloxane bonds in their main chains. Oligomers, aminoplast resins modified from aminoplast resins with many reactive groups in small molecules (meth)acrylate oligomers, or molecules such as novolak-type epoxy resins, bisphenol-type epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, etc. An oligomer having a cationically polymerizable functional group therein can be used.

As photopolymerizable monomers, (meth)acrylic monomers (b1) having reactive groups listed in the section of (meth)acryloyl unit (B), ethylenically unsaturated monomers and molecules other than (b1) are used. An ethylenically unsaturated compound (b2) having a group capable of reacting with the above-mentioned reactive group and a polyfunctional (meth)acrylate can be used, among which polyfunctional (meth)acrylate is preferred.
The polyfunctional (meth)acrylate is not particularly limited as long as it is a (meth)acrylate having two or more ethylenically unsaturated bonds in the molecule; for example, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, etc. Acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol dihydroxypivalate (meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate ) acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified pentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate , propylene oxide modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, propionic acid modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate Acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and ethylene oxide-modified bisphenol A diacrylate.

The polymerizable compound (D) is preferably a polyfunctional (meth)acrylate or urethane (meth)acrylate from the viewpoint of stretchability, scratch resistance, adhesive strength, and flexibility of the resin layer formed from the resin composition. It is an oligomer. These polymerizable compounds (D) may be used alone or in combination of two or more.

<Manufacture of resin composition>
The resin composition of the present invention can be obtained by mixing the urethane-acrylic composite resin (C) and the polymerizable compound (D). The mixing method is not particularly limited, and the solvent may be removed during mixing under reduced pressure or normal pressure. In the resin composition of the present invention, the polymerizable components in the resin composition can be crosslinked by active energy rays such as ultraviolet rays and electron beams. When crosslinking with ultraviolet rays, it is preferable to use a photopolymerization initiator, and a polymerization accelerator or sensitizer may also be used in combination.

(Photopolymerization initiator)
Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, α,α-dimethoxy-α- Phenylacetophenone, methylphenylglyoxylate, ethyl phenylglyoxylate, 4,4-bis(dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, Carbonyl compounds such as 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one; Sulfur compounds such as tetramethylthiuram disulfide and tetramethylthiuram disulfide; azobisisobutyronitrile, azobis Examples include azo compounds such as -2,4-dimethylvaleronitrile; peroxide compounds such as benzoyl peroxide and ditertiary butyl peroxide; phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; . Further, as the photopolymerization initiator, hydrogen abstraction type radical initiators such as acetophenone, benzophenone, benzyl, Michler's ketone, thioxanthone, and anthraquinone may be used. In that case, trimethylamine, triethylamine, tripropylamine, tributylamine, N - Tertiary amines such as methyldiethanolamine and p-dimethylaminophenyl alkyl ester may be used in combination.
Among them, carbonyl compounds and phosphine oxide compounds are preferred. These may be used alone or in combination of two or more.
The amount of photopolymerization initiator used is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 25 parts by weight, based on 100 parts by weight of the total solid content of the resin composition.

(sensitizer)
Examples of the sensitizer include unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, Thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium Derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaryloporphyrazine derivatives, naphthalocyanine derivatives , subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler ketone derivatives, and biimidazole derivatives. ``Pigment Handbook'' (1986, Kodansha), edited by Shin Okawara et al., ``Chemistry of Functional Pigments'' (CMC, 1981, edited by Shin Okawara et al.), ``Special Functional Materials'' (edited by Tadazaburo Ikemori et al.) Examples include sensitizers described in CMC (1986). In addition to these, a sensitizer that absorbs light in the ultraviolet to near-infrared region may be used. These may be used alone or in combination of two or more.
The amount of the sensitizer is preferably 0.1 to 150 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the photopolymerization initiator.

The content of the polymerizable compound (D) is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on the total 100 parts by weight of the solid content of the resin composition. A content of 10 to 90 parts by mass is preferable because the resin layer formed from the resin composition has excellent stretchability and scratch resistance.

The mass ratio of the urethane/acrylic composite resin (C) to the polymerizable compound (D) (mass of the urethane/acrylic composite resin (C):mass of the polymerizable compound (D)) is preferably 1:6 to 6: 1, more preferably 1:4 to 5:1. If it is within the above range, the resin layer formed from the resin composition will have excellent extensibility, scratch resistance, adhesive strength, and flexibility, which is preferable.

<Adhesive>
The resin composition of the present invention can be used as an adhesive. When used as an adhesive, further organic or inorganic fillers, reaction accelerators, silane coupling agents, phosphoric acid or phosphoric acid derivatives, leveling agents or antifoaming agents, fillers, propellants, plasticizers, superplasticizers, Known additives such as wetting agents, flame retardants, viscosity modifiers, preservatives, stabilizers, and coloring agents, solvents, etc. may be blended. These may be used alone or in combination of two or more.

As the organic or inorganic filler, polymers, ceramics, metals, metal oxides, metal salts, dyes and pigments, etc. can be used. The shape of the organic or inorganic filler is not particularly limited, and may be particulate or fibrous. In addition, when blending the polymer, softeners, plasticizers, flame retardants, storage stabilizers, antioxidants, ultraviolet absorbers, thixotropy agents, dispersion stabilizers, fluidity agents, antifoaming agents, etc. It is also possible to dissolve, semi-dissolve or microdisperse in the resin composition, not as a filler, but as a polymer blend, polymer alloy.

Examples of the silane coupling agent include trialkoxysilanes having a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane; 3-aminopropyltriethoxysilane, N-(2-aminoethyl)3-aminopropyltrimethoxysilane; Trialkoxysilane having an amino group such as silane; trialkoxysilanes having isocyanate groups such as 3-isocyanatepropyltriethoxysilane; trialkoxysilanes having mercapto groups such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; .
The content of the silane coupling agent is preferably 0.05 to 10 parts by mass based on 100 parts by mass of the solid content of the urethane-acrylic composite resin (C).

Among phosphoric acid or phosphoric acid derivatives, phosphoric acid may be any phosphoric acid having at least one free oxygen acid, such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, hypophosphoric acid, etc. Condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid; Examples of phosphoric acid derivatives include those obtained by partially esterifying the above-mentioned phosphoric acid with an alcohol while leaving at least one free oxygen acid. Examples of these alcohols include aliphatic alcohols such as methanol, ethanol, ethylene glycol, and glycerin, and aromatic alcohols such as phenol, xylenol, hydroquinone, catechol, and phloroglycinol.
The content of phosphoric acid or its derivative is preferably 0.005 to 5 parts by mass based on 100 parts by mass of the solid content of the urethane-acrylic composite resin (C) in the resin composition.

Among the leveling agents and antifoaming agents, examples of leveling agents include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, and polyetherester-modified hydroxyl group-containing polydimethylsiloxane. Examples include polydimethylsiloxane, acrylic copolymers, methacrylic copolymers, polyether-modified polymethylalkylsiloxanes, acrylic acid alkyl ester copolymers, methacrylic acid alkyl ester copolymers, and lecithin.
Examples of antifoaming agents include known ones such as silicone resins, silicone solutions, and copolymers of alkyl vinyl ethers, acrylic acid alkyl esters, and methacrylic acid alkyl esters.

<Coating agent>
The resin composition of the present invention can be used as a coating agent. When used as a coating agent, organic or inorganic fillers, solvents, other additives, etc. may be used in combination.

The coating agent can provide gloss adjustment and abrasion resistance by containing an organic or inorganic filler. Examples of organic fillers include resins such as epoxy resins, melamine resins, urea resins, acrylic resins, polyimide resins, fluororesins, polyethylene resins, polyester resins, and polyamide resins, which are polymerized into fine particles until they become insoluble in solvents. Examples of inorganic fillers include alumina, talc, silica, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, precipitated barium sulfate, precipitated barium carbonate, zirconium oxide, titanium oxide, and zinc oxide. , antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), phosphorous-doped tin oxide (PTO), barium titanate, barium sulfate, and smectite. From the viewpoint of imparting scratch resistance, optical properties, and design, inorganic fillers are preferred, and more preferred are alumina, silica, titanium oxide, zirconium oxide, antimony-doped tin oxide, tin-doped indium oxide, phosphorous-doped tin oxide, and oxidized tin. Zinc and magnesium fluoride are preferred, and alumina, silica, titanium oxide, and zirconium oxide are more preferred.

The inorganic filler may have a reactive functional group on its surface or may be untreated. Examples of the reactive functional group include ethylenically unsaturated bonds such as vinyl groups, (meth)acryloyl groups, and allyl groups, as well as epoxy groups and silanol groups. Examples of the shape of the inorganic filler include spheres, ellipsoids, polyhedrons, and scales, and these shapes are preferably uniform and regular particles. Further, the average particle diameter of the inorganic filler is preferably in the range of 0.005 to 100 μm, more preferably 0.01 to 50 μm, and still more preferably 0.01 to 25 μm.

Other additives include resins, dyes, pigment dispersants, oxygen scavengers and reducing agents such as phosphine, phosphonates, and phosphites, antifoggants, antifading agents, antihalation agents, optical brighteners, and surfactants. agents, plasticizers, flame retardants, antioxidants, dye precursors, ultraviolet absorbers, foaming agents, antifungal agents, antistatic agents, magnetic materials, storage stabilizers such as silane coupling agents and quaternary ammonium chloride, and surface In addition to tension adjusting agents, slipping agents, anti-blocking agents, light stabilizers, leveling agents, antifoaming agents, infrared absorbers, thixotropic agents, and antibacterial agents, agents that impart various properties can be mentioned.

<Laminated body>
A laminate can be obtained by providing a resin layer, which is a cured product of the resin composition of the present invention, on a base material. The method for forming the resin layer is not particularly limited, and for example, the resin composition may be applied onto a base material, heated if necessary to remove the solvent, and then irradiated with active energy rays to cure the resin composition. It can be formed by Alternatively, the resin composition is applied onto the first base material, heated if necessary to remove the solvent, and then bonded to the second base material, and then irradiated with active energy rays to remove the resin composition. By curing, a laminate having a resin layer between the base materials may be formed.
The temperature at which the solvent is removed is preferably in the range of 50°C to 200°C. The thickness of the resin layer is not particularly limited, but is preferably 0.1 μm to 300 mm.

Active energy rays refer to energy rays in a broad sense, including ultraviolet rays, visible light, infrared rays, electron beams, and radiation, that can provide the energy necessary for activation to cause a chemical reaction. As a light source for imparting active energy rays, a light source or electron beam having a main emission wavelength in a wavelength range of 100 nm to 550 nm is preferable. Examples of light sources having a main emission wavelength in the wavelength range from 100 nm to 550 nm include ultra-high-pressure mercury lamps, high-pressure mercury lamps, medium-pressure mercury lamps, mercury-xenon lamps, metal halide lamps, high-power metal halide lamps, xenon lamps, and pulsed light emission. Xenon lamp, deuterium lamp, fluorescent lamp, ND-YAG triple harmonic laser, HE-CD laser, nitrogen laser, XE-Cl excimer laser, XE-F excimer laser, semiconductor excited solid-state laser, emission wavelengths of 365 nm, 375 nm, 385 nm An example is an LED lamp light source having the following. In this specification, definitions of ultraviolet rays, visible light, near-infrared rays, etc. are based on "Iwanami Physical and Chemical Dictionary 4th Edition" edited by Ryogo Kubo et al. (Iwanami, 1987).

Examples of the base material include metals such as aluminum, thermoplastic polymers such as polyethylene, polylopylene, polyurethane, polyacrylate and polycarbonate and their copolymers, thermosetting polymers such as vulcanized rubber, urea-formaldehyde foam, melamine resin, Examples include wood, carbon fiber reinforced plastics, glass fiber reinforced plastics, and other fiber reinforced plastics, and the base materials bonded via the resin layer may be the same or different.

The resin composition of the present invention has excellent scratch resistance, elongation, adhesive strength, and flexibility, and is used in fields such as film base materials, adhesives, coating agents, elastomers, medical materials, and optical materials. It is useful in

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the following Examples do not limit the scope of the present invention in any way. In addition, unless otherwise specified, "parts" in the examples represent "parts by mass" and "%" represent "% by mass."

[Number average molecular weight (Mn)]
For the number average molecular weight, the polystyrene equivalent molecular weight was used when Shodex GPCLF-604 (manufactured by Shodex) was used as a column and THF was used as the developing solvent on a GPC equipped with an RI detector (GPC-104, manufactured by Shodex). .

<Manufacture of urethane/acrylic composite resin, etc.>
[Production Example 1] Urethane/acrylic composite resin (C-1)
(Step 1) P-1000 (product name, general name: bifunctional polypropylene glycol, hydroxyl value 110, manufactured by ADEKA) 100 as a polyol was placed in a reaction vessel equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, and a reflux device. 1 part, 28.3 parts of isophorone diisocyanate as a polyisocyanate, and 0.02 parts of titanium diisopropoxy bis(ethyl acetoacetate) as a catalyst were charged and stirred uniformly, and then reacted at 110°C for 5 hours under a nitrogen atmosphere to separate both ends. A urethane unit having an isocyanate group was obtained.
(Step 2) Cool the obtained product to 80°C, add 68.4 parts of methyl ethyl ketone as a solvent and 4.3 parts of 2-aminoethanethiol as a chain transfer agent, and react at 75°C for 2 hours. A urethane prepolymer having sulfanyl groups at both ends was obtained. The end point of the reaction was confirmed by FT-IR by the disappearance of the peak derived from the isocyanate group (around 2270 cm ⁻¹ ).
(Step 3) 4.9 parts of glycidyl methacrylate as the (meth)acrylic monomer (b1) having a reactive group and 19 parts of n-butyl methacrylate as the other ethylenically unsaturated monomer were added to the obtained composition. After adding 6 parts and stirring uniformly, the temperature was raised to 75° C. under a nitrogen atmosphere. Next, 0.1 part of 2,2'-azobis(2,4-dimethylvaleronitrile) was added as a polymerization initiator in 13 portions every 30 minutes, and the reaction was continued for an additional 2 hours after the addition of the polymerization initiator.
(Step 4) Then, after cooling to room temperature, the inside of the reaction vessel was switched to an oxygen atmosphere, and 2. By adding 5 parts of p-methoxyphenol, 0.2 parts of p-methoxyphenol, and 0.5 parts of N,N'-dimethylbenzylamine, and further reacting at 105°C for 10 hours, a urethane-acrylic composite resin with a solid content concentration of 70% ( C-1) was obtained.

[Production Example 2] Urethane/acrylic composite resin (C-2)
(Step 1) First, add polyol P-1000 (product name, general name: bifunctional polypropylene glycol, hydroxyl value 110, manufactured by ADEKA) to a reaction vessel equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, and a reflux device. 100 parts, 28.3 parts of isophorone diisocyanate as a polyisocyanate, and 0.02 parts of titanium diisopropoxy bis(ethyl acetoacetate) as a catalyst were charged, stirred uniformly, and then reacted at 110°C for 5 hours under a nitrogen atmosphere to form a mixture at both ends. A urethane unit having an isocyanate group was obtained.
(Step 2) Cool the obtained product to 80°C, add 68.7 parts of methyl ethyl ketone as a solvent and 4.3 parts of 2-aminoethanethiol as a chain transfer agent, and react at 75°C for 2 hours. A urethane prepolymer having sulfanyl groups at both ends was obtained. The end point of the reaction was confirmed by FT-IR by the disappearance of the peak derived from the isocyanate group.
(Step 3) Add 4.5 parts of 2-hydroxyethyl methacrylate as the (meth)acrylic monomer (b1) having a reactive group to the obtained composition, and n-butyl as the other ethylenically unsaturated monomer. After adding 18.1 parts of methacrylate and stirring uniformly, the temperature was raised to 75° C. under a nitrogen atmosphere. Next, 0.1 part of 2,2'-azobis(2,4-dimethylvaleronitrile) was added as a polymerization initiator in 13 portions every 30 minutes, and the reaction was continued for an additional 2 hours after the addition of the polymerization initiator.
(Step 4) Then, after cooling to room temperature, the inside of the reaction vessel was switched to an oxygen atmosphere, and 2-isocyanatoethyl 4.9 parts of acrylate, 0.02 parts of titanium diisopropoxy bis(ethyl acetoacetate), and 0.2 parts of p-methoxyphenol were added, and the mixture was further reacted at 60°C for 8 hours to achieve a solid concentration of 70%. A urethane/acrylic composite resin (C-2) was obtained. The end point of the reaction was confirmed by FT-IR by the disappearance of the peak derived from the isocyanate group.

[Production Examples 3 to 27] Urethane/acrylic composite resin (C-3 to C-27)
Urethane/acrylic composite resins (C-3 to C-27) were obtained by carrying out the same operation as in Production Example 2, except for changing the composition shown in Table 1.

[Comparative production example 1] Urethane/acrylic composite resin (C-28)
(Step 1) First, add polyol P-1000 (product name, general name: bifunctional polypropylene glycol, hydroxyl value 110, manufactured by ADEKA) to a reaction vessel equipped with a nitrogen gas inlet tube, a stirring device, a thermometer, and a reflux device. 100 parts, 28.3 parts of isophorone diisocyanate as a polyisocyanate, and 0.02 parts of titanium diisopropoxy bis(ethyl acetoacetate) as a catalyst were charged and stirred uniformly, and then reacted at 110°C for 5 hours under a nitrogen atmosphere. A urethane unit having an isocyanate group at the end was obtained.
(Step 2) The obtained product was cooled to 80°C, 68.9 parts of methyl ethyl ketone and 4.3 parts of 2-aminoethanethiol were added as a chain transfer agent, and reacted at 75°C for 2 hours to A urethane prepolymer having sulfanyl groups was obtained. The end point of the reaction was confirmed by FT-IR by the disappearance of the peak derived from the isocyanate group.
(Step 3) 28.2 parts of n-butyl methacrylate as another ethylenically unsaturated monomer was added to the obtained composition, stirred uniformly, and then heated to 75° C. under a nitrogen atmosphere. Next, 0.1 part of 2,2'-azobis(2,4-dimethylvaleronitrile) was added as a polymerization initiator in 13 portions every 30 minutes, and after the addition of the polymerization initiator, the reaction was further continued for 2 hours. A urethane/acrylic composite resin (C-28) with a solid content concentration of 70% was obtained.

[Comparative Production Example 2] Urethane resin (C-29)
In a reaction vessel equipped with a nitrogen gas inlet tube, a stirring device, a thermometer, and a reflux device, 100 parts of ADEKA Polyether P-1000 (product name, general name: bifunctional polypropylene glycol, hydroxyl value 110, manufactured by ADEKA) as a polyol was added. , 16.8 parts of isophorone diisocyanate as a polyisocyanate and 0.02 part of titanium diisopropoxy bis(ethyl acetoacetate) as a reaction accelerator were charged, stirred uniformly, and reacted at 110°C for 5 hours under a nitrogen atmosphere to form urethane. Resin was obtained. Next, 50.0 parts of methyl ethyl ketone was added and thoroughly stirred and mixed to obtain a urethane resin (C-29) with a solid content concentration of 70%.

[Comparative Production Example 3] Acrylic resin (C-30)
5.2 parts of methyl ethyl ketone, 8.0 parts of n-butyl methacrylate, and 2.0 parts of 2-hydroxyethyl methacrylate were added to a reaction vessel equipped with a nitrogen gas inlet tube, a stirring device, a thermometer, and a refluxer and stirred uniformly. Thereafter, the temperature was raised to 75° C. under a nitrogen atmosphere. Next, 0.1 part of 2,2'-azobis(2,4-dimethylvaleronitrile) was added as a polymerization initiator in 13 portions every 30 minutes, and the reaction was continued for an additional 2 hours after the addition of the polymerization initiator. Thereafter, after cooling to room temperature, the inside of the reaction vessel was switched to an oxygen atmosphere, and 2-isocyanatoethyl acrylate was added as the ethylenically unsaturated compound (b2) having a group capable of reacting with the above-mentioned reactive group in the molecule. 2 parts of titanium diisopropoxy bis(ethyl acetoacetate) and 0.2 parts of p-methoxyphenol were added, and the mixture was further reacted at 60°C for 8 hours to form an acrylic resin with a solid content of 70% ( C-30) was obtained. The end point of the reaction was confirmed by FT-IR by the disappearance of the peak derived from the isocyanate group.

The content of the urethane unit (A) in the obtained resin, the content of the structural unit having an ethylenically unsaturated double bond in the (meth)acryloyl unit, and the number average molecular weight of the urethane-acrylic composite resin are shown in Table 1. That's right.

The abbreviations listed in Table 1 are shown below.
・P-1000: Bifunctional polypropylene glycol, hydroxyl value 110, manufactured by ADEKA ・P-2000: Bifunctional polypropylene glycol, hydroxyl value 56, manufactured by ADEKA ・PTG-1000SN: Bifunctional polytetramethylene glycol, hydroxyl value 110, Manufactured by Hodogaya Chemical Industry Co., Ltd. GI-1000: Bifunctional polybutadiene polyol hydride, hydroxyl value 67.2, manufactured by Nippon Soda Co., Ltd. C-1090: Bifunctional polycarbonate polyol, hydroxyl value 114.8, manufactured by Kuraray Co., Ltd., P- 1010: Bifunctional polyester polyol, hydroxyl value 111.7, manufactured by Kuraray Co., Ltd. IPDI: Isophorone diisocyanate MEK: Methyl ethyl ketone GMA: Glycidyl methacrylate HEMA: 2-hydroxyethyl methacrylate HEAA: N-(2-hydroxyethyl) acrylamide・MOI: 2-isocyanatoethyl methacrylate ・BMA: n-butyl methacrylate ・AAEM: 2-acetoacetoxyethyl methacrylate ・NIPAM: Isopropylacrylamide ・HO-MS (N): 2-methacryloyloxyethyl succinic acid ・AA: Acrylic Acid/AOI: 2-isocyanatoethyl acrylate/HEA: 2-hydroxyethyl acrylate/PET3A: Pentaerythritol triacrylate/DPPA: Dipentaerythritol pentaacrylate

<Preparation of resin composition (1)>
[Example 1] Resin composition (1)-1
50 parts of urethane-acrylic composite resin (C-1) in solid content, 50 parts of pentaerythritol triacrylate in solid content as polymerizable compound (D), and ESACURE ONE (manufactured by IGM Resins) as a photopolymerization initiator.2. 5 parts of a mixed solvent of methyl ethyl ketone/propylene glycol monomethyl ether acetate = 1/1 (mass ratio) were mixed with a disper to obtain a resin composition (1)-1 with a solid content concentration of 25%.

[Examples 2 to 33, Comparative Examples 1 to 5] Resin compositions (1)-2 to 38
Resin compositions (1)-2 to 38 were obtained by carrying out the same operation as in Example 1 except for changing the formulation composition (solid content) shown in Tables 2 and 3.

[Comparative Example 6] Resin composition (1)-39
100 parts of pentaerythritol triacrylate in solid content as a polymerizable compound (D), 2.5 parts of ESACUREONE (manufactured by IGM Resins) as a photopolymerization initiator, methyl ethyl ketone/propylene glycol monomethyl ether acetate = 1/1 (mass ratio) The mixed solvents were mixed using a disper to obtain a resin composition (1)-39 having a solid content concentration of 25%.

<Evaluation of resin composition (1)>
The obtained resin composition (1) was evaluated as follows. The results are shown in Tables 2 and 3.

[Scratch resistance test]
After coating the resin composition (1) on a PET base material (thickness 100 μm: "Cosmoshine A4100" manufactured by Toyobo Co., Ltd.) using a bar coater, it is dried at 80 ° C. for 1 minute using a hot air dryer. As a result, a film with a thickness of 5 μm was obtained. The obtained film was cured by irradiating active energy rays to obtain a test piece. The obtained test piece was scratched 10 times using #0000 steel wool under a load of 300 g/cm ² , and then the presence or absence of scratches was visually observed and evaluated according to the following criteria. Ultraviolet light (UV) or electron beam (EB) was used as the active energy ray. The irradiation conditions are as follows.
For ultraviolet irradiation: High pressure mercury lamp 120W/cm ² -400mJ/cm ²
For electron beam irradiation: 125kV-30kGy (judgment criteria)
S: Number of scratches is 2 or less (very good)
A: There are 3 to 4 scratches (good)
B: Number of scratches is 5 to 6 (usable)
C: Number of scratches is 7 or more (unusable)

[Extensibility test]
The resin composition (1) was coated on a polycarbonate base material (thickness 1 mm: "Iupilon Sheet NF-2000" manufactured by Mitsubishi Gas Chemical Co., Ltd.) using a bar coater, and then heated at 80°C using a hot air dryer. A film with a thickness of 5 μm was obtained by drying for 1 minute. The obtained film was cured by irradiating active energy rays to obtain a test piece. The obtained test piece was cut into a dumbbell shape conforming to the JIS K6251-1 standard to obtain an extensibility test piece. The distance between chucks is 4 cm and the width is 1 cm. Using the obtained extensibility test piece, a tensile test was conducted at room temperature at a tensile speed of 100 mm/min using "EZ-SX" manufactured by Shimadzu Corporation. Using the inter-chuck distance of 4 cm as a reference, the cured film was visually checked for scratches when pulled to 4.0 cm, which corresponds to 100% of the original length, and evaluated using the following criteria.
Ultraviolet light (UV) or electron beam (EB) was used as the active energy ray. The irradiation conditions are as follows.
For ultraviolet irradiation: High pressure mercury lamp 120W/cm ² -400mJ/cm ²
For electron beam irradiation: 125kV-30kGy
(Judgment criteria)
S: Number of scratches is 3 or less (very good)
A: Number of scratches is 4 to 7 (good)
B: Number of scratches is 8 to 10 (usable)
C: The number of scratches is 11 or more (unusable)

Abbreviations in Tables 2 and 3 are shown below.
・PET3A: Pentaerythritol triacrylate ・UV7650B: "Shiko UV7650B" manufactured by Mitsubishi Chemical Corporation, urethane acrylate oligomer ・ESACURE ONE: "ESACURE ONE" manufactured by IGM Resins

<Preparation of resin composition (2)>
[Example 34] Resin composition (2)-1
50 parts of urethane-acrylic composite resin (C-1) in solid content, 50 parts of purple UV3000B (product name, general name: urethane acrylate, manufactured by Mitsubishi Chemical Corporation) as polymerizable compound (D) in solid content, photopolymerization Resin composition (2)-1 was obtained by adding 2.5 parts of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, "Irgacure 184") as an initiator, stirring, and removing the solvent under reduced pressure. .

[Examples 35 to 66 and Comparative Examples 7 to 11] Resin compositions (2)-2 to 38
Resin compositions (2)-2 to 38 were obtained by carrying out the same operation as in Example 33, except that the compositions were changed to those shown in Tables 4 and 5.

[Comparative Example 12] Resin composition (2)-39
As a polymerizable compound (D), 100 parts of Shiko UV3000B (product name, general name: urethane acrylate, manufactured by Mitsubishi Chemical Corporation) was used as a solid content, and as a photopolymerization initiator, 1-hydroxycyclohexylphenyl ketone (manufactured by BASF Corporation, "Irgacure 184") was used as a photopolymerization initiator. '') was added and stirred, and the solvent was removed under reduced pressure to obtain a resin composition (2)-39.

<Evaluation of resin composition (2)>
The obtained resin composition (2) was evaluated as follows. The results are shown in Tables 4 and 5.

[Adhesive strength]
Two prism sheets (prism sheet manufactured by Nippon Tokushu Optical Resin Co., Ltd., trade name: "LPV90-1.0", material: poly(methyl methacrylate)), which are polyacrylic transparent films, were prepared as base materials. After corona treatment was performed on the back surface of the first prism sheet (the surface without prisms) at a discharge rate of 300 W min/m ² , resin composition (2) was applied to a thickness of 1 μm. did. Next, the front side (prism surface) of the second prism sheet was laminated so that the optical axis of the first prism sheet and the optical axis of the second prism sheet were perpendicular to each other to obtain a laminate. Next, active energy rays are irradiated from the back side of the second prism sheet of the obtained laminate to cure the resin composition (2), thereby forming the first prism sheet/resin layer/second prism sheet configuration. A laminate was obtained. Ultraviolet light (UV) or electron beam (EB) was used as the active energy ray. The irradiation conditions are as follows.
For ultraviolet irradiation: High pressure mercury lamp 300W/cm ² -300mJ/cm ²
For electron beam irradiation: 125kV-30kGy

The adhesive strength was measured in accordance with JIS K6854-4 Adhesives - Peel adhesive strength testing method - Part 4: Floating roller method. Specifically, the obtained laminate was cut into a size of 25 mm x 150 mm, and the cut laminate was pasted on a metal plate using double-sided adhesive tape to obtain a laminate for measurement. . Regarding this measurement laminate, the peel strength when two prism sheets were peeled off at 23° C., 50% relative humidity, and a speed of 300 mm/min was measured, and evaluated based on the following criteria.
(Judgment criteria)
S: Peel strength is 3.0N/25mm or more (very good)
A: Peel strength is 1.0 N/25 mm or more and less than 3.0 N/25 mm (good)
B: Peel strength is 0.5 N/25 mm or more and less than 1.0 N/25 mm (usable)
C: Peel strength is less than 0.5N/25mm (unusable)

[Flexibility]
Resin composition (2) was filled into a sheet-like mold with a thickness of 500 μm, the surface was prepared, and after aging at 60° C. for 1 day, it was irradiated with active energy rays to be cured. The obtained cured product was punched out using a dumbbell mold to obtain a dumbbell-shaped test piece. Using this dumbbell-shaped test piece, a tensile test was conducted at a tensile speed of 50 mm/min, the elongation rate (%) at break was measured, and the results were evaluated based on the following criteria.
Ultraviolet light (UV) or electron beam (EB) was used as the active energy ray. The irradiation conditions are as follows.
For ultraviolet irradiation: High pressure mercury lamp 300W/cm ² -500mJ/cm ²
For electron beam irradiation: 125kV-50kGy
(Judgment criteria)
S: Elongation at break is 150% or more (very good)
A: Elongation at break is 125% or more and less than 150% (good)
B: Elongation at break is 100% or more and less than 125% (usable)
C: Elongation at break is less than 100% (unusable)

Abbreviations in Tables 4 and 5 are shown below.
・UV-3000B: "Shiko UV-3000B" manufactured by Mitsubishi Chemical Corporation Urethane acrylate oligomer ・DCPA: Tricyclodecane dimethanol diacrylate ・Irgacure 184: manufactured by BASF Photopolymerization initiator, 1-hydroxycyclohexylphenyl ketone

From the results in Tables 2 to 5, the resin composition of the present invention was excellent in adhesiveness, scratch resistance (coating film strength), extensibility, and flexibility.

Claims (6)

A urethane-acrylic composite resin (C) in which a urethane unit (A) and a (meth)acryloyl unit (B), which are reaction products of a polyol and a polyisocyanate, are connected by a chain transfer agent residue, and a photopolymerizable compound (D). ) A resin composition containing
The (meth)acryloyl unit (B) contains a polymer of an ethylenically unsaturated monomer containing a (meth)acrylic monomer (b1) having a reactive group, and a group capable of reacting with the reactive group. A polymer containing a structural unit having an ethylenically unsaturated double bond, which is produced by a reaction with an ethylenically unsaturated compound (b2) having
The photopolymerizable compound (D) is an epoxy (meth)acrylate oligomer, a urethane (meth)acrylate oligomer, a polyester (meth)acrylate oligomer, a polyether (meth)acrylate oligomer, or an acrylic (meth)acrylate oligomer. and polyfunctional (meth)acrylate. The resin composition according to claim 1, wherein the urethane unit (A) and the (meth)acryloyl unit (B) are connected by a residue of a chain transfer agent having an amino group. The resin composition according to claim 1 or 2, wherein the content of the structural unit having an ethylenically unsaturated double bond is 20 to 85 parts by mass in 100 parts by mass of the (meth)acryloyl unit (B). The resin composition according to any one of claims 1 to 3, wherein the content of the urethane unit (A) is 45 to 90 parts by mass in 100 parts by mass of the urethane/acrylic composite resin (C). The resin composition according to any one of claims 1 to 4, wherein the urethane-acrylic composite resin (C) has a number average molecular weight of 8,000 to 50,000. A laminate comprising, on a base material, a resin layer which is a cured product of the resin composition according to any one of claims 1 to 5.