JP2021084971A - (meth)acrylate resin, curable resin composition, cured product and article - Google Patents

Abstract

To provide a (meth)acrylate resin which enables formation of a cured product that has excellent heat resistance and adhesion to a base material and is excellent in low elasticity.SOLUTION: The (meth)acrylate resin contains: as essential reactive raw materials, a copolymer (I) that is composed of a polymer containing a (meth)acrylate compound (A) and a polymerizable unsaturated bond-containing compound (B) having a reactive functional group other than the (meth)acrylate compound (A), as essential polymerization components; and a polymerizable unsaturated bond-containing compound (C) other than the (meth)acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B) that has a functional group that can react with a reactive functional group that the polymerizable unsaturated bond-containing compound (B) has. The (meth)acrylate compound (A) contains a specific phenol compound as a raw material.SELECTED DRAWING: None

Description

The present invention provides a (meth) acrylate resin having excellent heat resistance and substrate adhesion and capable of forming a cured product having excellent low elasticity, a curable resin composition containing the same, and the curable resin composition. The present invention relates to a cured product of the above and an article having a coating film of the cured product.

In recent years, curable compositions such as active energy ray-curable compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting compositions that can be cured by heat have been introduced into inks, paints, coating agents, adhesives, and optics. It is widely used in the field of materials and the like. Among them, as the coating agent application, generally, it is possible to impart designability to the surface of various base materials, have excellent curability, and form a coating film capable of preventing deterioration of the base material surface. Is required. Furthermore, in recent years, there has been a demand from the industrial world for a material capable of forming a cured coating film having not only curability but also performance such as heat resistance at a level capable of protecting an object to be coated even under various temperature environments. Has been done.

As a technique for improving the heat resistance of the cured coating film, a curable composition containing a di (meth) acrylate represented by the following general formula (1) is known (see, for example, Patent Document 1). ).

〔式（１）において、Ｒ_１は、水素原子又はメチル基を表す。〕

[In formula (1), R ₁ represents a hydrogen atom or a methyl group. ]

However, the curable composition has insufficient heat resistance in the cured coating film, and does not satisfy the increasingly demanding performance in terms of substrate adhesion and low elasticity.

Therefore, there has been a demand for a material having excellent heat resistance and adhesion to a base material and capable of forming a cured product having excellent low elasticity.

Japanese Unexamined Patent Publication No. 2005-314320

The problem to be solved by the present invention is a (meth) acrylate resin having excellent heat resistance and substrate adhesion and capable of forming a cured product having excellent low elasticity, a curable resin composition containing the same, and a curable resin composition containing the same. The present invention provides an article having a cured product of the curable resin composition and a coating film of the cured product.

As a result of diligent studies to solve the above problems, the present inventors have made a polymerizable unsaturated compound having a reactive functional group other than the specific (meth) acrylate compound (A) and the (meth) acrylate compound (A). A functional group capable of reacting with a copolymer (I) composed of a polymer containing a saturated bond-containing compound (B) as an essential polymerization component and a reactive functional group of the polymerizable unsaturated bond-containing compound (B). It has been found that the above-mentioned problems can be solved by using the above-mentioned (meth) acrylate compound (A) and the polymerizable unsaturated bond-containing compound (C) other than the above-mentioned polymerizable unsaturated bond-containing compound (B). The present invention has been completed.

That is, the present invention contains the (meth) acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B) having a reactive functional group other than the (meth) acrylate compound (A) as essential polymerization components. The (meth) acrylate compound (A) and the said compound having a functional group capable of reacting with the copolymer (I) composed of the polymer to be produced and the reactive functional group of the polymerizable unsaturated bond-containing compound (B). A (meth) acrylate resin using a polymerizable unsaturated bond-containing compound (C) other than the polymerizable unsaturated bond-containing compound (B) as an essential reaction raw material, wherein the (meth) acrylate compound (A) is , The phenolic hydroxyl group-containing compound (a1), the cyclic carbonate compound (a2-1) or the cyclic ether compound (a2-2), and the unsaturated monocarboxylic acid (a3) are essential reaction raw materials. A (meth) acrylate resin characterized in that the phenolic hydroxyl group-containing compound (a1) is a phenol compound having at least three hydroxyl groups as substituents on the aromatic ring, a curable resin composition containing the same, the above-mentioned. It relates to a cured product of a curable resin composition and an article having a cured coating film of the cured product.

The (meth) acrylate resin of the present invention contains the (meth) acrylate compound and a photopolymerization initiator because it has excellent heat resistance and substrate adhesion and can form a cured product having excellent low elasticity. The curable resin composition can be used as a coating agent or an adhesive, and can be particularly preferably used as a coating agent.

The (meth) acrylate resin of the present invention is a (meth) acrylate compound (A) and a polymerizable unsaturated bond-containing compound (B) having a reactive functional group other than the (meth) acrylate compound (A) (hereinafter, hereinafter. A copolymer (I) composed of a polymer containing "polymerizable unsaturated bond-containing compound (B)" as an essential polymerization component, and the polymerizable unsaturated bond-containing compound (B). A polymerizable unsaturated bond-containing compound (C) other than the (meth) acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B) having a functional group capable of reacting with a reactive functional group (hereinafter, "" It is abbreviated as "polymerizable unsaturated bond-containing compound (C)"), which is an essential reaction raw material.

In the present invention, "(meth) acrylate" means acrylate and / or methacrylate. Further, "(meth) acryloyl" means acryloyl and / or methacryloyl. Further, "(meth) acrylic" means acrylic and / or methacrylic.

The copolymer (I) is composed of a polymer containing the (meth) acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B) as essential polymerization components.

Examples of the (meth) acrylate compound (A) include a phenolic hydroxyl group-containing compound (a1), a cyclic carbonate compound (a2-1) or a cyclic ether compound (a2-2), and an unsaturated monocarboxylic acid (a3). Is used as an essential reaction raw material.

As the phenolic hydroxyl group-containing compound (a1), a phenol compound having at least three hydroxyl groups as a substituent on the aromatic ring is essentially contained.

The phenol compound having at least three hydroxyl groups as the substituent on the aromatic ring is not particularly limited as long as it has three hydroxyl groups as the substituent on the aromatic ring, and has other substituents. May be good.

Examples of the phenol compound having at least three hydroxyl groups as the substituent on the aromatic ring include compounds represented by the following structural formulas (1-1) to (1-3).

In the structural formulas (1-1) to (1-3), R ¹ is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom. .. Further, p is 0 or an integer of 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, and further preferably 0. q is an integer of 3 or more. The position of the substituent on the aromatic ring in the above structural formula is arbitrary. For example, in the naphthalene ring of the structural formula (1-2), it may be substituted on any ring, and the structural formula (1) In 1-3), it is shown that it may be substituted on any ring of the benzene ring existing in one molecule, and it is shown that the number of substituents in one molecule is p and q.

Among the compounds represented by the above structural formulas (1-1) to (1-3), trihydroxybenzene having p of 0 and q of 3 in the structural formula (1-1) has excellent heat resistance. It is preferable because a (meth) acrylate resin capable of forming a cured product having properties, substrate adhesion and low elasticity can be obtained, and more specifically, 1, which has hydroxyl groups at the 1-position, 2-position and 3-position. More preferably, 2,3-trihydroxybenzene (hereinafter, may be referred to as "pyrogallol") or 1,2,4-trihydroxybenzene having hydroxyl groups at the 1-position, 2-position and 4-position.

Examples of the cyclic carbonate compound (a2-1) include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate and the like. These cyclic carbonate compounds may be used alone or in combination of two or more. Further, among these, ethylene carbonate or propylene carbonate is preferable because a (meth) acrylate resin capable of forming a cured product having excellent heat resistance, substrate adhesion and low elasticity can be obtained.

Examples of the cyclic ether compound (a2-2) include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more. Further, among these, ethylene oxide or propylene oxide is preferable because a (meth) acrylate resin capable of forming a cured product having excellent heat resistance, substrate adhesion and low elasticity can be obtained.

The molar ratio of the phenolic hydroxyl group-containing compound (a1) to the cyclic carbonate compound (a2-1) [(a2-1) / (a1)], or the phenolic hydroxyl group-containing compound (A) and the cyclic ether. The molar ratio with compound (a2-2) [(a2-2) / (a1)] gives a (meth) acrylate resin capable of forming a cured product having excellent heat resistance, substrate adhesion and low elasticity. Therefore, it is preferably 3 or more.

The unsaturated monocarboxylic acid (a3) refers to a compound having a (meth) acryloyl group and a carboxyl group in one molecule, and examples thereof include acrylic acid and methacrylic acid. Further, as the unsaturated monocarboxylic acid (a3), a compound represented by the following structural formula (2) can also be used. Further, an esterified product of the unsaturated monocarboxylic acid (a3), an acid halide, an acid anhydride and the like can also be used. These unsaturated monocarboxylic acids (a3) can be used alone or in combination of two or more.

［式中Ｘは、炭素数１〜１０のアルキレン鎖、ポリオキシアルキレン鎖、（ポリ）エステル鎖、芳香族炭化水素鎖、または（ポリ）カーボネート鎖を表し、構造中にハロゲン原子やアルコキシ基等を有していても良い。Ｙは、水素原子またはメチル基である。］

[X in the formula represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly) ester chain, an aromatic hydrocarbon chain, or a (poly) carbonate chain, and has a halogen atom, an alkoxy group, or the like in the structure. May have. Y is a hydrogen atom or a methyl group. ]

Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

Examples of the (poly) ester chain include a (poly) ester chain represented by the following structural formula (3).

（式中Ｒ_１は、炭素原子数１〜１０のアルキレン基であり、ｎは１〜５の整数である。）

(In the formula, R ₁ is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.)

Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain and the like. Further, as a partial structure, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring can also be used.

Examples of the (poly) carbonate chain include a (poly) carbonate chain represented by the following structural formula (4).

（式中Ｒ_２は、炭素原子数１〜１０のアルキレン基であり、ｎは１〜５の整数である。）

(In the formula, R ₂ is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.)

Examples of the esterified product of the unsaturated monocarboxylic acid (a3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth). (Meta) acrylic acid alkyl ester compounds such as n-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; Hydroxyl-containing (meth) acrylic acid ester compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, diethylamino (meth) acrylate Nitrogen-containing (meth) acrylate compounds such as ethyl; to glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholyl (meth) acrylate, isobornyl (meth) acrylate, cyclo (meth) acrylate Other (meth) acrylic acid ester compounds such as xyl may be mentioned.

Examples of the acid halide of the unsaturated monocarboxylic acid (a3) include (meth) acrylic acid chloride and the like.

Examples of the acid anhydride of the unsaturated monocarboxylic acid (a3) include (meth) acrylic anhydride and the like.

The molar ratio of the cyclic carbonate compound (a2-1) to the unsaturated monocarboxylic acid (a3) [(a3) / (a2-1)], or the cyclic ether compound (a2-2) and the unsaturated With the molar ratio [(a3) / (a2-2)] to the monocarboxylic acid (a3), a (meth) acrylate resin capable of forming a cured product having excellent heat resistance, substrate adhesion and low elasticity can be obtained. Therefore, it is preferably 0.65 or more, and more preferably in the range of 0.65 to 1.05.

The weight average molecular weight of the (meth) acrylate compound (A) is 1,000 or less because a (meth) acrylate resin capable of forming a cured product having excellent heat resistance, substrate adhesion and low elasticity can be obtained. Is preferable.

In the present invention, the weight average molecular weight (Mw) indicates a value measured by a gel permeation chromatography (GPC) method.

The method for producing the (meth) acrylate compound (A) is not particularly limited, and the (meth) acrylate compound (A) can be appropriately produced by a known method. For example, it may be produced by a method of reacting all of the reaction raw materials at once, or by a method of sequentially reacting the reaction raw materials. Among them, since the reaction can be easily controlled, the phenolic hydroxyl group-containing compound (a1) and the cyclic carbonate compound (a2-1) or the cyclic ether compound (a2-2) are first added in the presence of a basic catalyst. It can be carried out by reacting in a temperature range of 60 to 200 ° C. and then reacting an unsaturated monocarboxylic acid (a3) or an esterified product thereof in a temperature range of 60 to 140 ° C. in the presence of an acidic catalyst. it can. This reaction can be carried out under reduced pressure, normal pressure, or pressure.

As the polymerizable unsaturated bond-containing compound (B), a compound having a reactive functional group is used. In the present invention, the "polymerizable unsaturated bond" means an unsaturated bond capable of radical polymerization.

Examples of the reactive functional group include a hydroxyl group, an epoxy group, an isocyanate group, a carboxyl group, an acrylamide group and the like. These reactive functional groups may have alone or may have two or more kinds.

Examples of the polymerizable unsaturated bond-containing compound (B) include a hydroxyl group-containing (meth) acrylate compound, an epoxy group-containing (meth) acrylate compound, an isocyanate group-containing (meth) acrylate compound, a carboxyl group-containing compound, and an acrylamide group. Examples thereof include compounds having. These polymerizable unsaturated bond-containing compounds (B) can be used alone or in combination of two or more.

Examples of the hydroxyl group-containing (meth) acrylate compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolpropanedi (meth) acrylate, and pentaerythritol (meth) acrylate. , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) Examples thereof include acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane (meth) acrylate, ditrimethylolpropane di (meth) acrylate, and ditrimethylolpropanetri (meth) acrylate. In addition, (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains were introduced into the molecular structures of the various hydroxyl group-containing (meth) acrylate compounds (). Poly) oxyalkylene modified products, lactone modified products in which a (poly) lactone structure is introduced into the molecular structure of the various hydroxyl group-containing (meth) acrylate compounds, and the like can also be used. These hydroxyl group-containing (meth) acrylate compounds may be used alone or in combination of two or more.

Examples of the epoxy group-containing (meth) acrylate compound include glycidyl group-containing (meth) acrylate monomers such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and epoxycyclohexylmethyl (meth) acrylate. Examples thereof include mono (meth) acrylate compounds of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These epoxy group-containing (meth) acrylate compounds may be used alone or in combination of two or more.

Examples of the isocyanate group-containing (meth) acrylate compound include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate. These isocyanate group-containing (meth) acrylate compounds may be used alone or in combination of two or more.

Examples of the carboxyl group-containing compound include (meth) acrylic acid, ω-carboxy-polycaprolactone monoacrylate and the like. These carboxyl group-containing compounds may be used alone or in combination of two or more.

Examples of the acrylamide group-containing compound include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, and N-ethoxyethyl. Examples thereof include (meth) acrylamide and N-butoxyethyl (meth) acrylamide. The acrylamide group-containing compound may be used alone or in combination of two or more.

The copolymer (I) may contain other polymerization components other than the (meth) acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B), if necessary.

Examples of the other polymerization components include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl ( Alicyclic mono (meth) acrylate compounds such as meta) acrylate and octyl (meth) acrylate; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate; Heterocyclic mono (meth) acrylate compounds such as tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxy. Mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds such as ethyl (meth) acrylate, phenoxybenzyl (meth) acrylate, and phenylphenoxyethyl (meth) acrylate: molecules of the various mono (meth) acrylate monomers. A (poly) oxyalkylene-modified mono (meth) acrylate compound in which a polyoxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the structure; A lactone-modified mono (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the (meth) acrylate compound; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate. , Hexadiol di (meth) acrylate, neopentyl glycol di (meth) acrylate and other aliphatic di (meth) acrylate compounds; 1,4-cyclohexanedimethanol di (meth) acrylate, norbornandi (meth) acrylate, norbornandi Alicyclic di (meth) acrylate compounds such as methanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate; biphenol di (meth) acrylate, bisphenol di (meth) acrylate. ) Aromatic di (meth) acrylate compounds such as acrylates; (poly) oxyethylene chains, (poly) oxyethylene chains in the molecular structure of the various di (meth) acrylate compounds. Polyoxyalkylene-modified di (meth) acrylate compounds introduced with (poly) oxyalkylene chains such as poly) oxypropylene chains and (poly) oxytetramethylene chains; A lactone-modified di (meth) acrylate compound introduced with a poly) lactone structure; an aliphatic tri (meth) acrylate compound such as trimethylolpropantri (meth) acrylate and glycerin tri (meth) acrylate; A (poly) oxyalkylene-modified tri (meth) acrylate compound in which a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the molecular structure of the compound. A lactone-modified tri (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the aliphatic tri (meth) acrylate compound; pentaerythritol tetra (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, di A tetrafunctional or higher functional aliphatic poly (meth) acrylate compound such as pentaerythritol hexa (meth) acrylate; in the molecular structure of the aliphatic poly (meth) acrylate compound, a (poly) oxyethylene chain, a (poly) oxypropylene chain, A tetrafunctional or higher functional (poly) oxyalkylene-modified poly (meth) acrylate compound introduced with a (poly) oxyalkylene chain such as a (poly) oxytetramethylene chain; Examples thereof include a tetrafunctional or higher functional lactone-modified poly (meth) acrylate compound having a poly) lactone structure introduced therein.

The method for producing the copolymer (I) is not particularly limited, and any method may be used for producing the copolymer (I). For example, a method obtained by polymerizing all of the polymerization components containing the (meth) acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B) at 50 to 200 ° C. can be mentioned. ..

In the polymerization, a polymerization initiator can be used if necessary.

Examples of the polymerization initiator include radical polymerization initiators such as persulfate, organic peroxide, and hydrogen peroxide, 4,4'-azobis (4-cyanovaleric acid), and 2,2'-azobis ( Examples thereof include an azo initiator such as 2-amidinopropane) dihydrochloride. Further, the radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent such as ascorbic acid, for example. These polymerization initiators can be used alone or in combination of two or more.

Examples of the persulfate include potassium persulfate, sodium persulfate, ammonium persulfate and the like. These persulfates can be used alone or in combination of two or more.

Examples of the organic peroxide include diacyl peroxides such as benzoyl peroxide, lauroyl peroxide and decanoyl peroxide, dialkyl peroxides such as t-butylcumyl peroxide and dicumyl peroxide, and t-butyl peroxide. Peroxyesters such as -2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, hydroperoxides such as cumenehydroperoxide, paramentanhydroperoxide, t-butylhydroperoxide, etc. And so on. These organic peroxides can be used alone or in combination of two or more.

The amount of the polymerization initiator used may be an amount that allows the polymerization to proceed smoothly, but the polymerization containing the (meth) acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B). The range of 0.1 to 20 parts by mass is preferable, and the range of 0.5 to 10 parts by mass is more preferable with respect to 100 parts by mass of the total components.

The polymerizable unsaturated bond-containing compound (C) has a functional group capable of reacting with the reactive functional group of the polymerizable unsaturated bond-containing compound (B).

Examples of the polymerizable unsaturated bond-containing compound (C) include those similar to those exemplified as the above-mentioned polymerizable unsaturated bond-containing compound (B), but the polymerizable unsaturated bond-containing compound ( When a hydroxyl group-containing (meth) acrylate compound is used as B), it is preferable to use an isocyanate group-containing (meth) acrylate compound and / or an acrylamide group-containing compound as the polymerizable unsaturated bond-containing compound (C), and polymerization is preferable. When an epoxy group-containing (meth) acrylate compound is used as the sex unsaturated bond-containing compound (B), it is preferable to use a carboxyl group-containing compound as the polymerizable unsaturated bond-containing compound (C), and the polymerizable unsaturated bond is preferably used. When an isocyanate group-containing (meth) acrylate compound is used as the bond-containing compound (B), it is preferable to use a hydroxyl group-containing (meth) acrylate as the polymerizable unsaturated bond-containing compound (C), and a polymerizable unsaturated bond is used. When a carboxyl group-containing compound is used as the contained compound (B), it is preferable to use an epoxy group-containing (meth) acrylate as the polymerizable unsaturated bond-containing compound (C), and the polymerizable unsaturated bond-containing compound (B). When an acrylamide group-containing compound is used as the), it is preferable to use a hydroxyl group-containing (meth) acrylate as the polymerizable unsaturated bond-containing compound (C). These polymerizable unsaturated bond-containing compounds (C) can be used alone or in combination of two or more.

The method for producing the (meth) acrylate resin of the present invention is not particularly limited, and any method may be used for producing the (meth) acrylate resin. For example, a method of collectively reacting all of the reaction raw materials containing the copolymer (I) and the polymerizable unsaturated bond-containing compound (C) can be mentioned.

As a method of reacting all of the reaction raw materials at once, for example, a reaction raw material containing the copolymer (I) and the polymerizable unsaturated bond-containing compound (C) is used as a basic catalyst or an acidic catalyst. Examples thereof include a method obtained by reacting at 50 to 150 ° C. in the presence.

Examples of the basic catalyst include N-methylmorpholin, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), and 1,5-diazabicyclo [4.3.0] nonen-. 5 (DBN), 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1 -Methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3-( Amine compounds such as 2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane and tetramethylammonium hydroxide; and four such as trioctylmethylammonium chloride and trioctylmethylammonium acetate. Class ammonium salts; phosphines such as trimethylphosphine, tributylphosphine, triphenylphosphine; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl (2-hydroxylpropyl) phosphonium Phosphonium salts such as chloride, triphenylphosphonium chloride, benzylphosphonium chloride; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, Organic tin compounds such as 1,1,3,3-tetrabutyl-1,3-dodecanoyl distanoxane; organic metal compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octanate; inorganic metal compounds And so on. These basic catalysts can be used alone or in combination of two or more.

Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid and oxalic acid, and Lewis acids such as boron trifluoride, aluminum chloride and zinc chloride. And so on. These acidic catalysts can be used alone or in combination of two or more.

The (meth) acrylate resin of the present invention can be used as a curable resin composition by adding a photopolymerization initiator.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2-. Hydroxy-2-methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, diphenyl (2,4,6-trimethoxybenzoyl) phosphenyl Oxide, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphenyl oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone and the like can be mentioned.

Examples of commercially available products of the other photopolymerization initiator include "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", and "Omnirad-379". , "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-2100" Omnirad-754 "," Omnirad-784 "," Omnirad-500 "," Omnirad-81 "(manufactured by IGM)," Kayacure-DETX "," Kayacure-MBP "," Kayacure-DMBI "," Kayacure-EPA " , "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure-10", "Vicure-55" (manufactured by Stofa Chemical Co., Ltd.), "Trigonal P1" (manufactured by Akzo), "Sandray 1000" Sands), "Deep" (Apjon), "QuantaCure-PDO", "QuantaCure-ITX", "QuantaCure-EPD" (Ward Blenkinsop), "Runtecure-1104" (Runtec) (Manufactured by the company) and the like.

The amount of the photopolymerization initiator added is preferably in the range of 1 to 20% by mass in the curable resin composition, for example.

The curable resin composition of the present invention comprises the (meth) acrylate compound (A), the polymerizable unsaturated bond-containing compound (B), and the polymerizable unsaturated bond-containing compound as long as the effects of the present invention are not impaired. It may contain other (meth) acrylate compound (D) other than (C).

Examples of the other (meth) acrylate compound (D) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth). Acrylate mono (meth) acrylate compounds such as acrylate, 2-ethylhexyl (meth) acrylate and octyl (meth) acrylate; alicyclic mono (meth) acrylate such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate. (Meta) acrylate compound; heterocyclic mono (meth) acrylate compound such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxy (meth) ) Acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, phenylphenoxyethyl (meth) acrylate and other aromatic products. Mono (meth) acrylate compounds such as (meth) acrylate compounds: (poly) oxyethylene chains, (poly) oxypropylene chains, (poly) oxytetramethylene chains, etc. in the molecular structure of the various mono (meth) acrylate monomers. (Poly) oxyalkylene-modified mono (meth) acrylate compound introduced with the polyoxyalkylene chain of the above; lactone-modified mono (meth) acrylate having a (poly) lactone structure introduced into the molecular structure of the various mono (meth) acrylate compounds. Compounds; aliphatic di (meth) such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate. Acrylate compounds; 1,4-cyclohexanedimethanol di (meth) acrylate, norbornandi (meth) acrylate, norbornan dimethanol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, tricyclodecanedimethanol di (meth) ) Alicyclic di (meth) acrylate compounds such as acrylate; biphenol di (meth) acrylate, bisphenol di (meth) acrylate, etc. Aromatic di (meth) acrylate compound; (poly) oxy such as (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain in the molecular structure of the various di (meth) acrylate compounds. Polyoxyalkylene-modified di (meth) acrylate compound introduced with an alkylene chain; lactone-modified di (meth) acrylate compound with a (poly) lactone structure introduced into the molecular structure of the various di (meth) acrylate compounds; trimethylolpropane An aliphatic tri (meth) acrylate compound such as tri (meth) acrylate and glycerin tri (meth) acrylate; a (poly) oxyethylene chain and a (poly) oxypropylene chain in the molecular structure of the aliphatic tri (meth) acrylate compound. , (Poly) oxyalkylene-modified tri (meth) acrylate compound introduced with (poly) oxyalkylene chain such as (poly) oxytetramethylene chain; (poly) lactone in the molecular structure of the aliphatic tri (meth) acrylate compound. A lactone-modified tri (meth) acrylate compound having a structure introduced; a tetrafunctional or higher aliphatic poly (meth) such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropantetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Acrylic compound: A (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain was introduced into the molecular structure of the aliphatic poly (meth) acrylate compound 4 Functional or higher (poly) oxyalkylene-modified poly (meth) acrylate compound; a tetrafunctional or higher functional lactone-modified poly (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the aliphatic poly (meth) acrylate compound. And so on.

Further, as the other (meth) acrylate compound (D), in addition to the above-mentioned one, a phenol compound other than the phenol compound having at least three hydroxyl groups as a substituent on the aromatic ring (hereinafter, “other phenol compound”). A (meth) acrylate compound containing a cyclic carbonate compound or a cyclic ether compound and an unsaturated monocarboxylic acid as essential reaction raw materials can be used.

Examples of the other phenolic compounds include cresol, xylenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, 1-naphthol, 2-naphthol, and 1,3-naphthalenediol. , 1,5-Naphtholene diol, 2,6-naphthalene diol, 2,7-naphthalene diol, hydrogenated bisphenol, hydrogenated biphenol, polyphenylene ether type diol, polynaphthylene ether type diol, phenol novolac resin, cresol novolak resin, Examples thereof include bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, cycloring structure-containing phenol resin and the like.

As the cyclic carbonate compound and the cyclic ether compound, the same compounds as the above-mentioned cyclic carbonate compound (a2-1) and the above-mentioned cyclic ether compound (a2-2) can be used.

As the unsaturated monocarboxylic acid, the same as the unsaturated monocarboxylic acid (a3) described above can be used.

Further, examples of the other (meth) acrylate compound (D) include an epoxy resin having a (meth) acryloyl group, a urethane resin having a (meth) acryloyl group, an acrylic resin having a (meth) acryloyl group, and (meth). ) Amidoimide resin having an acryloyl group, acrylamide resin having a (meth) acryloyl group and the like.

The content of the other (meth) acrylate compound (D) is preferably 90% by mass or less in the curable resin composition of the present invention.

The curable resin composition of the present invention may contain an organic solvent for the purpose of adjusting the coating viscosity, and the type and amount of the organic solvent added may be appropriately selected and adjusted according to the desired performance.

Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone and isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; aromatics such as toluene, xylene and solvent naphtha. Group solvent; Alicyclic solvent such as cyclohexane and methylcyclohexane; Alcohol solvent such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol Examples thereof include glycol ether solvents such as monoalkyl ether acetate. These organic solvents can be used alone or in combination of two or more.

In addition, the curable resin composition of the present invention includes various types of epoxy resin, inorganic fine particles, polymer fine particles, pigments, antifoaming agents, viscosity modifiers, leveling agents, flame retardants, storage stabilizers, etc., as required. It can also contain additives.

Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. Bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, naphthol-cresol co-shrink novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Examples thereof include reactive epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, and oxazolidone type epoxy resin. These epoxy resins can be used alone or in combination of two or more.

Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy. Examples include resin.

Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin. Examples include resin.

Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'. -Biphenol type epoxy resin and the like can be mentioned.

Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, and hydrogenated tetramethyl-4,4'-biphenol type epoxy resin. , Hydrogenated tetramethyl-2,2'-biphenol type epoxy resin and the like.

Since the curable resin composition of the present invention can form a cured product having excellent heat resistance, substrate adhesion and low elasticity, it can be used as a coating agent or an adhesive, and is particularly preferably used as a coating agent. Can be done.

The cured product of the present invention can be obtained by irradiating the curable resin composition with active energy rays. Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, they may be irradiated in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently carry out the curing reaction by ultraviolet rays.

As the ultraviolet source, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specific examples thereof include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

Integrated light quantity of the active energy ray is not particularly limited, it is preferably from 50 to 5000 mJ / cm ^2, more preferably 100~1000mJ / cm ^2. When the integrated light amount is in the above range, it is preferable because the generation of the uncured portion can be prevented or suppressed.

The irradiation of the active energy rays may be performed in one step or may be divided into two or more steps.

The article of the present invention has a coating film made of the cured product. Examples of the article include plastic molded products such as mobile phones, home appliances, automobile interior / exterior materials, and OA equipment, semiconductor devices, display devices, imaging devices, and the like.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

In this example, the weight average molecular weight (Mw) is a value measured under the following conditions using a gel permission chromatograph (GPC).

Measuring device; HLC-8220 manufactured by Tosoh Corporation
Column; Guard column H _XL- H manufactured by Tosoh Corporation
+ TSKgel G5000HXL manufactured by Tosoh Corporation
+ TSKgel G4000HXL manufactured by Tosoh Corporation
+ TSKgel G3000HXL manufactured by Tosoh Corporation
+ TSKgel G2000HXL manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing: SC-8010 manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow velocity 1.0 ml / min Standard; Polystyrene sample; 0.4 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

(Synthesis Example 1: Production of (Meta) Acrylate Compound (A-1))
To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 126 parts by mass of pyrogallol, 277 parts by mass of ethylene carbonate, and 0.7 parts by mass of a 50% potassium hydroxide aqueous solution were added, and 20 parts at 170 ° C. under a nitrogen atmosphere. Reacted for time. Next, after dissolving the obtained reaction product in 333 parts by mass of toluene, 228 parts by mass of acrylic acid, 5.0 parts by mass of paratoluenesulfonic acid, and 0.2 parts by mass of methylhydroquinone were charged, air was blown into the mixture, and the mixture was stirred. However, the reaction was carried out at 100 ° C. for 10 hours. Then, the mixture was cooled to 50 ° C., the obtained reaction solution was washed with water, and toluene was removed to obtain a (meth) acrylate compound (A-1). The weight average molecular weight (Mw) of this (meth) acrylate compound (A-1) was 620, and the viscosity at 25 ° C. was 330 mPa · s. The viscosity is a value measured under 25 ° C. conditions using an E-type rotational viscometer (“RE80U” manufactured by Toki Sangyo Co., Ltd.). Further, the molar ratio of pyrogallol to ethylene carbonate [(ethylene carbonate) corresponding to the molar ratio [(a2-1) / (a1)] of the phenolic hydroxyl group-containing compound (a1) to the cyclic carbonate compound (a2-1)]. (Number of moles of pyrogallol) / (number of moles of pyrogallol)] is 3.15, and the molar ratio of the cyclic carbonate compound (a2-1) to the unsaturated carboxylic acid (a3) [(a3) / (a2-1). ], The molar ratio of ethylene carbonate to acrylic acid [(number of moles of acrylic acid) / (number of moles of ethylene carbonate)] was 1.004.

(Synthesis Example 2: Production of (Meta) Acrylate Compound (A-2))
To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 126 parts by mass of pyrogallol, 337 parts by mass of propylene carbonate, and 0.7 parts by mass of a 50% potassium hydroxide aqueous solution were added, and 30 parts at 170 ° C. under a nitrogen atmosphere. Reacted for time. Next, after dissolving the obtained reaction product in 379 parts by mass of toluene, 237 parts by mass of acrylic acid, 5.7 parts by mass of paratoluenesulfonic acid, and 0.2 parts by mass of methylhydroquinone were charged, air was blown into the mixture, and the mixture was stirred. However, the reaction was carried out at 100 ° C. for 20 hours. Then, the mixture was cooled to 50 ° C., the obtained reaction solution was washed with water, and toluene was removed to obtain a (meth) acrylate compound (A-2). The weight average molecular weight (Mw) of this (meth) acrylate compound (A-2) was 780, and the viscosity at 25 ° C. was 500 mPa · s. Further, the molar ratio of pyrogallol to propylene carbonate corresponding to the molar ratio of the phenolic hydroxyl group-containing compound (a1) to the cyclic carbonate compound (a2-1) [(a2-1) / (a1)] [(propylene carbonate). (Number of moles of pyrogallol) / (number of moles of pyrogallol)] is 3.30, and the molar ratio of the cyclic carbonate compound (a2-1) to the unsaturated carboxylic acid (a3) [(a3) / (a2-1). ], The molar ratio of propylene carbonate to acrylic acid [(number of moles of acrylic acid) / (number of moles of propylene carbonate)] was 0.994.

(Synthesis Example 3: Production of (Meta) Acrylate Compound (A-3))
To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 126 parts by mass of pyrogallol, 277 parts by mass of ethylene carbonate, and 0.7 parts by mass of a 50% potassium hydroxide aqueous solution were added, and 20 parts at 170 ° C. under a nitrogen atmosphere. Reacted for time. Next, after dissolving the obtained reaction product in 282 parts by mass of toluene, 152 parts by mass of acrylic acid, 4.2 parts by mass of paratoluenesulfonic acid, and 0.1 parts by mass of methylhydroquinone were charged, air was blown into the mixture, and the mixture was stirred. However, the reaction was carried out at 100 ° C. for 10 hours. Then, the mixture was cooled to 50 ° C., the obtained reaction solution was washed with water, and toluene was removed to obtain a (meth) acrylate compound (A-3). The weight average molecular weight (Mw) of this (meth) acrylate compound (A-3) was 580, and the viscosity at 25 ° C. was 520 mPa · s. Further, the molar ratio of pyrogallol to ethylene carbonate [(ethylene carbonate) corresponding to the molar ratio [(a2-1) / (a1)] of the phenolic hydroxyl group-containing compound (a1) to the cyclic carbonate compound (a2-1)]. (Number of moles of pyrogallol) / (number of moles of pyrogallol)] is 3.15, and the molar ratio of the cyclic carbonate compound (a2-1) to the unsaturated carboxylic acid (a3) [(a3) / (a2-1). ], The molar ratio of ethylene carbonate to acrylic acid [(number of moles of acrylic acid) / (number of moles of ethylene carbonate)] was 0.669.

(Synthesis Example 4: Production of (Meta) Acrylate Compound (A-4))
To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 126 parts by mass of pyrogallol, 277 parts by mass of ethylene carbonate, and 0.7 parts by mass of a 50% potassium hydroxide aqueous solution were added, and 20 parts at 170 ° C. under a nitrogen atmosphere. Reacted for time. Next, after dissolving the obtained reaction product in 277 parts by mass of toluene, 144 parts by mass of acrylic acid, 4.2 parts by mass of paratoluenesulfonic acid, and 0.1 parts by mass of methylhydroquinone were charged, air was blown into the mixture, and the mixture was stirred. However, the reaction was carried out at 100 ° C. for 10 hours. Then, the mixture was cooled to 50 ° C., the obtained reaction solution was washed with water, and toluene was removed to obtain a (meth) acrylate compound (A-4). The weight average molecular weight (Mw) of this (meth) acrylate compound (A-4) was 560, and the viscosity at 25 ° C. was 600 mPa · s. Further, the molar ratio of pyrogallol to ethylene carbonate [(ethylene carbonate) corresponding to the molar ratio [(a2-1) / (a1)] of the phenolic hydroxyl group-containing compound (a1) to the cyclic carbonate compound (a2-1)]. (Number of moles of pyrogallol) / (number of moles of pyrogallol)] is 3.15, and the molar ratio of the cyclic carbonate compound (a2-1) to the unsaturated carboxylic acid (a3) [(a3) / (a2-1). ], The molar ratio of ethylene carbonate to acrylic acid [(number of moles of acrylic acid) / (number of moles of ethylene carbonate)] was 0.636.

(Example 1: Production of (meth) acrylate resin (1))
54 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 23 parts by mass of methyl methacrylate, 5 parts by mass of the (meth) acrylate compound (A-1) obtained in Synthesis Example 1, 68 parts by mass of butyl acetate, and 5 parts by mass of perbutyl O were mixed in advance. It was added dropwise over 3 hours. After holding at 120 ° C. for 4 hours, 0.2 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 37 parts by mass of acrylic acid, and 0.7 parts by mass of triphenylphosphine were charged, and air was blown into the mixture while stirring. , 120 ° C. for 10 hours to obtain the desired (meth) acrylate resin (1). The solid acid value of the obtained (meth) acrylate resin (1) was 2 mgKOH / g, and the weight average molecular weight (Mw) was 14300.

(Example 2: Production of (meth) acrylate resin (2))
54 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 23 parts by mass of methyl methacrylate, 5 parts by mass of the (meth) acrylate compound (A-2) obtained in Synthesis Example 2, 68 parts by mass of butyl acetate, and 5 parts by mass of perbutyl O were mixed in advance. It was added dropwise over 3 hours. After holding at 120 ° C. for 4 hours, 0.2 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 37 parts by mass of acrylic acid, and 0.7 parts by mass of triphenylphosphine were charged, and air was blown into the mixture while stirring. , 120 ° C. for 10 hours to obtain the desired (meth) acrylate resin (2). The solid acid value of the obtained (meth) acrylate resin (2) was 2 mgKOH / g, and the weight average molecular weight (Mw) was 15050.

(Example 3: Production of (meth) acrylate resin (3))
54 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 23 parts by mass of methyl methacrylate, 5 parts by mass of the (meth) acrylate compound (A-3) obtained in Synthesis Example 3, 68 parts by mass of butyl acetate, and 5 parts by mass of perbutyl O were mixed in advance. It was added dropwise over 3 hours. After holding at 120 ° C. for 4 hours, 0.2 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 37 parts by mass of acrylic acid, and 0.7 parts by mass of triphenylphosphine were charged, and air was blown into the mixture while stirring. , 120 ° C. for 10 hours to obtain the desired (meth) acrylate resin (3). The solid acid value of the obtained (meth) acrylate resin (3) was 2 mgKOH / g, and the weight average molecular weight (Mw) was 13890.

(Example 4: Production of (meth) acrylate resin (4))
54 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 23 parts by mass of methyl methacrylate, 5 parts by mass of the (meth) acrylate compound (A-4) obtained in Synthesis Example 4, 68 parts by mass of butyl acetate, and 5 parts by mass of perbutyl O were mixed in advance. It was added dropwise over 3 hours. After holding at 120 ° C. for 4 hours, 0.2 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 37 parts by mass of acrylic acid, and 0.7 parts by mass of triphenylphosphine were charged, and air was blown into the mixture while stirring. , 120 ° C. for 10 hours to obtain the desired (meth) acrylate resin (4). The solid acid value of the obtained (meth) acrylate resin (4) was 2 mgKOH / g, and the weight average molecular weight (Mw) was 13340.

(Example 5: Production of (meth) acrylate resin (5))
54 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere. Next, 72 parts by mass of glycidyl methacrylate, 18 parts by mass of methyl methacrylate, 10 parts by mass of the (meth) acrylate compound (A-1) obtained in Synthesis Example 1, 68 parts by mass of butyl acetate, and 5 parts by mass of perbutyl O were mixed in advance. It was added dropwise over 3 hours. After holding at 120 ° C. for 4 hours, 0.2 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 37 parts by mass of acrylic acid, and 0.7 parts by mass of triphenylphosphine were charged, and air was blown into the mixture while stirring. , 120 ° C. for 10 hours to obtain the desired (meth) acrylate resin (5). The solid acid value of the obtained (meth) acrylate resin (5) was 2 mgKOH / g, and the weight average molecular weight (Mw) was 16340.

(Example 6: Production of (meth) acrylate resin (6))
54 parts by mass of dipropylene glycol monomethyl ether was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere. Next, 69 parts by mass of methacrylic acid, 26 parts by mass of methyl methacrylate, 5 parts by mass of the (meth) acrylate compound (A-1) obtained in Synthesis Example 1, 68 parts by mass of dipropylene glycol monomethyl ether, and 5 parts by mass of perbutyl O were added. It was mixed in advance and added dropwise over 3 hours. After holding at 120 ° C. for 4 hours, 66 parts by mass of dipropylene glycol monomethyl ether, 0.2 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 112 parts by mass of glycidyl methacrylate, and 0.8 parts by mass of triphenylphosphine were added. The mixture was charged, blown with air, and reacted at 110 ° C. for 20 hours with stirring to obtain the desired (meth) acrylate resin (6). The solid acid value of the obtained (meth) acrylate resin (6) was 3 mgKOH / g, and the weight average molecular weight (Mw) was 18760.

(Example 7: Production of (meth) acrylate resin (7))
54 parts by mass of dipropylene glycol monomethyl ether was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere. Next, 84 parts by mass of methacrylic acid, 11 parts by mass of methyl methacrylate, 5 parts by mass of the (meth) acrylate compound (A-1) obtained in Synthesis Example 1, 68 parts by mass of dipropylene glycol monomethyl ether, and 5 parts by mass of perbutyl O were added. It was mixed in advance and added dropwise over 3 hours. After holding at 120 ° C. for 4 hours, 46 parts by mass of dipropylene glycol monomethyl ether, 0.2 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 90 parts by mass of glycidyl methacrylate, and 0.8 parts by mass of triphenylphosphine were added. The mixture was charged, blown with air, and reacted at 110 ° C. for 15 hours with stirring to obtain the desired (meth) acrylate resin (7). The solid acid value of the obtained (meth) acrylate resin (7) was 102 mgKOH / g, and the weight average molecular weight (Mw) was 15840.

(Example 8: Production of (meth) acrylate resin (8))
54 parts by mass of dipropylene glycol monomethyl ether was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere. Next, 78 parts by mass of methacrylic acid, 17 parts by mass of methyl methacrylate, 5 parts by mass of the (meth) acrylate compound (A-1) obtained in Synthesis Example 1, 68 parts by mass of dipropylene glycol monomethyl ether, and 5 parts by mass of perbutyl O were added. It was mixed in advance and added dropwise over 3 hours. After holding at 120 ° C. for 4 hours, 46 parts by mass of dipropylene glycol monomethyl ether, 0.2 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 90 parts by mass of glycidyl methacrylate, and 0.8 parts by mass of triphenylphosphine were added. The mixture was charged, blown with air, and reacted at 110 ° C. for 15 hours with stirring to obtain the desired (meth) acrylate resin (8). The solid acid value of the obtained (meth) acrylate resin (8) was 82 mgKOH / g. The weight average molecular weight (Mw) was 14730.

(Example 9: Production of (meth) acrylate resin (9))
54 parts by mass of dipropylene glycol monomethyl ether was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere. Next, 72 parts by mass of methacrylic acid, 23 parts by mass of methyl methacrylate, 5 parts by mass of the (meth) acrylate compound (A-1) obtained in Synthesis Example 1, 68 parts by mass of dipropylene glycol monomethyl ether, and 5 parts by mass of perbutyl O were added. It was mixed in advance and added dropwise over 3 hours. After holding at 120 ° C. for 4 hours, 47 parts by mass of dipropylene glycol monomethyl ether, 0.2 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 90 parts by mass of glycidyl methacrylate, and 0.8 parts by mass of triphenylphosphine were added. The mixture was charged, blown with air, and reacted at 110 ° C. for 15 hours with stirring to obtain the desired (meth) acrylate resin (9). The solid acid value of the obtained (meth) acrylate resin (9) was 61 mgKOH / g, and the weight average molecular weight (Mw) was 13640.

(Comparative Example 1: Production of (Meta) Acrylate Resin (10))
54 parts by mass of butyl acetate was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120 ° C. under a nitrogen atmosphere. Next, 30 parts by mass of glycidyl methacrylate, 70 parts by mass of methyl methacrylate, 68 parts by mass of butyl acetate, and 5 parts by mass of perbutyl O were mixed in advance and added dropwise over 3 hours. After holding at 120 ° C. for 4 hours, 0.2 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 37 parts by mass of acrylic acid, and 0.7 parts by mass of triphenylphosphine were charged, and air was blown into the mixture while stirring. , 120 ° C. for 10 hours to obtain the desired (meth) acrylate resin (10). The solid acid value of the obtained (meth) acrylate resin (10) was 2 mgKOH / g.

(Example 10: Preparation of curable resin composition (1))
100 parts by mass of the (meth) acrylate resin (1) having a non-volatile content of 53% by mass obtained in Example 1 and 2.7 parts by mass of a photopolymerizable initiator (“Omnirad 907” manufactured by IGM) are mixed and curable. A resin composition (1) was obtained.

(Examples 11 to 16: Preparation of curable resin compositions (2) to (7))
Instead of the (meth) acrylate resin (1) used in Example 10, the (meth) acrylate resins (2) to (6) obtained in Examples 2 to 6 were used in the blending amounts shown in Table 1. Obtained curable resin compositions (2) to (7) in the same manner as in Example 10.

(Example 17: Preparation of curable resin composition (8))
100 parts by mass of the (meth) acrylate resin (7) having a non-volatile content of 53% by mass obtained in Example 7 and a bisphenol A type epoxy resin (“EPICLON 850S” manufactured by DIC Co., Ltd., epoxy equivalent: 188 g / equivalent) 21.7 2.7 parts by mass and 2.7 parts by mass of a photopolymerizable initiator (“Omnirad 907” manufactured by IGM) were mixed to obtain a curable resin composition (8).

(Examples 18 and 19: Preparation of curable resin compositions (9) and (10))
Instead of the (meth) acrylate resin (7) used in Example 17, the (meth) acrylate resins (8) and (9) obtained in Examples 8 and 9 were used in the blending amounts shown in Table 1. Obtained curable resin compositions (9) and (10) in the same manner as in Example 17.

(Comparative Example 2: Preparation of curable resin composition (C1))
100 parts by mass of the (meth) acrylate resin (10) having a non-volatile content of 53% by mass obtained in Comparative Example 1 and 2.7 parts by mass of a photopolymerizable initiator (“Omnirad 907” manufactured by IGM) are mixed and curable. A resin composition (C1) was obtained.

The following evaluations were carried out using the curable resin compositions obtained in the above Examples and Comparative Examples.

[Evaluation method of heat resistance]
The heat resistance was evaluated by measuring the glass transition temperature.

<Preparation of test piece 1>
The curable resin compositions (1) to (10) obtained in Examples and the curable resin compositions (C1) obtained in Comparative Examples were subjected to copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolysis) using an applicator. It was applied on a copper foil "F2-WS" 18 μm) so as to have a film thickness of 50 μm, and dried at 80 ° C. for 30 minutes. ^{Next, after irradiating with an ultraviolet ray of 1000 mJ / cm 2} using a metal halide lamp, the cured product was heated at 160 ° C. for 1 hour to peel off the cured product from the copper foil, and the cured product was used as a test piece 1.

<Measurement of glass transition temperature>
The test piece 1 is cut into a size of 6 mm × 35 mm, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Leometric Co., Ltd., tensile method: frequency 1 Hz, heating rate 3 ° C./min) is used. The temperature at which the change in viscoelasticity was maximized was evaluated as the glass transition temperature (hereinafter, abbreviated as "Tg"). The higher the Tg, the better the heat resistance.

[Evaluation method of substrate adhesion]
The substrate adhesion was evaluated by measuring the peel strength.
<Preparation of test piece 2>
The curable resin composition obtained in Examples and Comparative Examples was applied onto a copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) with a 50 μm applicator, and 1000 mJ / using a metal halide lamp. After irradiating with ultraviolet rays of cm ² , the test piece 2 was obtained by heating at 160 ° C. for 1 hour.

<Measuring method of peel strength>
The test piece 2 was cut into a size of 1 cm in width and 12 cm in length, and the 90 ° peel strength was measured using a peeling tester (“A & D Tencilon” manufactured by A & D Co., Ltd., peeling speed 50 mm / min).

[Evaluation method of elasticity]
The elasticity was evaluated by measuring the elastic modulus by a tensile test.

<Tensile test>
The test piece 1 was cut into a size of 10 mm × 80 mm, and a tensile test of the test piece was carried out under the following measurement conditions using a precision universal testing machine Autograph “AG-IS” manufactured by Shimadzu Corporation. The elastic modulus (MPa) until the test piece broke was measured and evaluated according to the following criteria.

Measurement conditions: temperature 23 ° C, humidity 50%, distance between marked lines 20 mm, distance between fulcrums 20 mm, tensile speed 10 mm / min

Table 1 shows the compositions and evaluation results of the curable resin compositions (1) to (10) obtained in Examples 10 to 19 and the curable resin composition (C1) obtained in Comparative Example 2.

The description of the mass part of the (meth) acrylate resin in Table 1 is the solid content value.

Examples 10 to 19 shown in Table 1 are examples using the (meth) acrylate resin of the present invention. It was confirmed that the cured product of the curable resin composition containing the (meth) acrylate resin of the present invention has excellent heat resistance and substrate adhesion, and has a low elastic modulus.

On the other hand, Comparative Example 2 is an example in which the (meth) acrylate compound (A) specified in the present invention is not used. Since this curable resin composition has low Tg, low peel strength, and high elastic modulus, it was confirmed that it is insufficient in heat resistance, substrate adhesion, and low elasticity.

Claims (10)

A copolymer consisting of a (meth) acrylate compound (A) and a polymer containing a polymerizable unsaturated bond-containing compound (B) having a reactive functional group other than the (meth) acrylate compound (A) as an essential polymerization component. Polymer (I) and
Polymerization other than the (meth) acrylate compound (A) and the polymerizable unsaturated bond-containing compound (B) having a functional group capable of reacting with the reactive functional group of the polymerizable unsaturated bond-containing compound (B). With the sex unsaturated bond-containing compound (C),
A (meth) acrylate resin that is an essential reaction raw material.
The (meth) acrylate compound (A) comprises a phenolic hydroxyl group-containing compound (a1), a cyclic carbonate compound (a2-1) or a cyclic ether compound (a2-2), and an unsaturated monocarboxylic acid (a3). It is an essential reaction raw material and is used.
A (meth) acrylate resin, wherein the phenolic hydroxyl group-containing compound (a1) is a phenolic compound having at least three hydroxyl groups as substituents on the aromatic ring. The (meth) acrylate resin according to claim 1, wherein the phenol compound having at least three hydroxyl groups as a substituent on the aromatic ring is 1,2,3-trihydroxybenzene or 1,2,4-trihydroxybenzene. The molar ratio of the phenolic hydroxyl group-containing compound (a1) to the cyclic carbonate compound (a2-1) [(a2-1) / (a1)], or the phenolic hydroxyl group-containing compound (a1) and the cyclic ether. The (meth) acrylate resin according to claim 1, wherein the molar ratio [(a2-2) / (a1)] to the compound (a2-2) is 3 or more. The molar ratio of the cyclic carbonate compound (a2-1) to the unsaturated monocarboxylic acid (a3) [(a3) / (a2-1)], or the cyclic ether compound (a2-2) and the unsaturated The (meth) acrylate resin according to claim 1, wherein the molar ratio [(a3) / (a2-2)] with the monocarboxylic acid (a3) is 0.65 or more. The (meth) according to claim 1, wherein the reactive functional group of the polymerizable unsaturated bond-containing compound (B) is at least one selected from the group consisting of a hydroxyl group, an epoxy group, an isocyanate group, a carboxyl group and an acrylamide group. ) Acrylate resin. A curable resin composition containing the (meth) acrylate resin according to any one of claims 1 to 5 and a photopolymerization initiator. The curable resin composition further comprises other (meth) compounds other than the (meth) acrylate compound (A), the polymerizable unsaturated bond-containing compound (B), and the polymerizable unsaturated bond-containing compound (C). The curable resin composition according to claim 6, which contains an acrylate compound (D). The curable resin composition according to claim 6, wherein the curable resin composition further contains a curing agent and / or an organic solvent. A cured product, which is a cured reaction product of the curable resin composition according to any one of claims 6 to 8. An article characterized by having a coating film made of the cured product according to claim 9.