JP2010260883A - Copolymer, resin composition containing the copolymer, and cured product thereof - Google Patents

Abstract

（式中、Ｒ¹は水素原子又はメチル基を示し、Ｘは炭素数１〜６の２価の炭化水素基を示す）で表されるビニル単量体Ａに対応するモノマー単位と、（４−ビニルフェニル）酢酸であるビニル単量体Ｂに対応するモノマー単位を少なくとも含む。
【選択図】なしThe present invention provides a copolymer that is excellent in solvent resistance and moisture absorption resistance and that can obtain a cured product having excellent adhesion to a substrate even when touched with a solvent.
The copolymer has the following formula (1):

(Wherein R ¹ represents a hydrogen atom or a methyl group, and X represents a divalent hydrocarbon group having 1 to 6 carbon atoms), and a monomer unit corresponding to the vinyl monomer A represented by (4 At least monomer units corresponding to vinyl monomer B which is -vinylphenyl) acetic acid.
[Selection figure] None

Description

  The present invention relates to a copolymer comprising a monomer unit corresponding to a vinylphenyl monomer having an epoxy group and a monomer unit corresponding to a vinylphenyl monomer having a carboxyl group, and a curable resin composition comprising the copolymer And a cured product obtained by curing the composition. The copolymer of the present invention can be used for paints, coating agents, adhesives, electronic materials (protective films, sealing materials, etc.) and the like.

  A polymer obtained by radical polymerization of an unsaturated monomer having a C—C double bond is widely used in various applications. If this polymer can be crosslinked by heat or light, it can be used as a functional polymer. It can also be used for applications. Conventionally, as a composition that can be cured by heat or light to form a cured coating film, a curable resin composition containing a polymer having an epoxy group in the side chain, a curable composition containing a polymer having an isocyanate group in the side chain A curable resin composition in which an acid, a base, an organometallic catalyst, or the like is added to a resin composition or a polymer containing an alkoxysilane group is known. However, cured coatings obtained from these curable resin compositions do not satisfy all required performance such as curability, adhesion to substrates, film hardness, heat resistance, chemical resistance, and storage stability. Can not.

  JP-A-2000-297082 discloses a Grignard reagent produced by reacting ω-haloalkyl-styrene or the like with metal magnesium for the purpose of improving the physical properties of a cured product, and obtained by reacting with epichlorohydrin or the like. Epoxy group-containing radical polymerizable compounds, monomers such as styrenes, dienes such as butadiene, (meth) acrylic esters such as methyl (meth) acrylate, and radical polymerizable compounds such as (meth) acrylic acid Copolymers containing as components have been proposed. However, the cured coating film obtained from the curable resin composition comprising this copolymer has insufficient performance in terms of solvent resistance, moisture absorption resistance, and adhesion to the substrate after being exposed to the solvent.

JP 2000-297082 A

  Accordingly, an object of the present invention is to provide a copolymer capable of obtaining a cured product excellent in solvent resistance, moisture absorption resistance, and adhesion to a substrate after being exposed to the solvent, and curability containing the copolymer. It is providing the resin composition and its hardened | cured material.

  As a result of intensive studies to achieve the above object, the present inventors have responded to a monomer unit corresponding to a vinylphenyl monomer having an epoxy group having a specific structure and a vinylphenyl monomer having a carboxyl group having a specific structure. When a curable resin composition containing a copolymer containing at least a monomer unit is applied to a substrate and cured, it is excellent in solvent resistance, moisture absorption resistance, and adhesion to the substrate after touching the solvent. The present inventors have found that a cured coating film can be obtained and completed the present invention.

（式中、Ｒ¹は水素原子又はメチル基を示し、Ｘは炭素数１〜６の２価の炭化水素基を示す）
で表されるビニル単量体Ａに対応するモノマー単位と、下記式（２）

で表されるビニル単量体Ｂに対応するモノマー単位を少なくとも含む共重合体を提供する。 That is, the present invention provides the following formula (1):

(Wherein R ¹ represents a hydrogen atom or a methyl group, and X represents a divalent hydrocarbon group having 1 to 6 carbon atoms)
A monomer unit corresponding to the vinyl monomer A represented by the following formula (2):

A copolymer containing at least a monomer unit corresponding to the vinyl monomer B represented by

（式中、Ｒ²は水素原子又はメチル基を示し、Ｒ³は炭素数が１〜２４の有機基を示す。ａは０又は１の整数である）
で表されるビニル単量体Ｃに対応するモノマー単位を含んでいてもよい。 The copolymer further includes the following formula (3):

(Wherein R ² represents a hydrogen atom or a methyl group, R ³ represents an organic group having 1 to 24 carbon atoms, a is an integer of 0 or 1)
The monomer unit corresponding to the vinyl monomer C represented by these may be included.

（式中、Ｒ⁴は炭素数１〜８の２価の脂肪族飽和炭化水素基を示す。Ｒ⁵はイソシアネート基のブロック剤Ｒ⁵Ｈの残基を示す）
で表される基、下記式（４ｂ）

（式中、Ｅは単結合又は２価の炭化水素基を示す。Ｒ⁶及びＲ⁷は、同一又は異なって、炭素数１〜６のアルキル基又は炭素数１〜６のアルコキシ基を示す。Ｒ⁸は炭素数１〜６のアルキル基を示す。ｂは１〜１０の整数である）
で表される基が挙げられる。 As R ³ in the above formula (3), the following formula (4a)

(Wherein, R ⁴ represents a divalent aliphatic saturated hydrocarbon to a group .R ⁵ is the residue of a blocking agent R ⁵ H isocyanate groups of 1 to 8 carbon atoms)
A group represented by formula (4b):

(In formula, E shows a single bond or a bivalent hydrocarbon group. R < ⁶ > and R < ⁷ > are the same or different, and show a C1-C6 alkyl group or a C1-C6 alkoxy group. R ⁸ represents an alkyl group having 1 to 6 carbon atoms, and b is an integer of 1 to 10)
The group represented by these is mentioned.

  The present invention also provides a curable resin composition in which a light and / or thermal polymerization initiator is blended with the copolymer.

  The curable resin composition may further contain a polyfunctional vinyl compound, a polyfunctional thiol compound, an epoxy compound, and / or an epoxy resin.

  The present invention further provides a cured product obtained by curing the curable resin composition.

  By curing the curable resin composition containing the copolymer of the present invention, it is possible to obtain a cured product having excellent solvent resistance and moisture absorption resistance and high adhesion even when touched with a solvent. Moreover, the curable resin composition containing the copolymer of this invention is excellent also in sclerosis | hardenability. Therefore, it can be used as a paint, a coating agent, an adhesive, and the like, and can be suitably used particularly in the field of electronic materials.

  The copolymer of the present invention includes a monomer unit corresponding to the vinylphenyl monomer A having an epoxy group represented by the formula (1) and a vinylphenyl monomer having a carboxyl group represented by the formula (2). And at least a monomer unit corresponding to B. When the curable resin composition containing this copolymer is cured by heat or active energy rays, the epoxy group and carboxyl group contribute to the curing, and are excellent in various physical properties, in particular, substrate adhesion and solvent resistance. Give a cured product. The copolymer of the present invention may be a random copolymer or a block copolymer.

[Vinyl monomer A]
In the vinyl monomer A represented by formula (1), R ¹ represents a hydrogen atom or a methyl group, X represents a divalent hydrocarbon group having 1 to 6 carbon atoms. Examples of the divalent hydrocarbon group having 1 to 6 carbon atoms include linear or branched alkylene groups such as methylene, ethylene, propylene, trimethylene, tetramethylene, ethylethylene, pentamethylene, and hexamethylene groups. Can be mentioned. Among these, a linear or branched alkylene group having a low carbon number (for example, 1 to 3 carbon atoms) such as a methylene group, an ethylene group, or a propylene group is particularly preferable.

  Examples of the vinyl monomer A represented by the formula (1) include 4-vinylbenzyloxirane represented by the following formula (5). 4-vinylbenzyl oxirane can be produced by reacting a Grignard reagent represented by the following formula (6) with epichlorohydrin. The Grignard reagent represented by the following formula (6) is obtained by reacting chlorostyrene and Grignard reaction magnesium.

  Examples of the vinyl monomer A represented by the formula (1) include 4-vinylphenethyloxirane represented by the following formula (7). 4-Vinylphenethyloxirane can be produced by reacting a Grignard reagent represented by the following formula (8) with epichlorohydrin. The Grignard reagent represented by the following formula (8) is obtained by reacting chloromethylstyrene with Grignard reaction magnesium.

  The proportion of the monomer unit corresponding to the vinyl monomer A in the copolymer of the present invention is, for example, 1 to 95% by weight, preferably 5 to 80% by weight, based on all monomer units constituting the copolymer. More preferably, it is 10 to 70% by weight. If this ratio is too small, the solvent resistance may decrease, and if it is too large, the adhesion may decrease.

[Vinyl monomer B]
The vinyl monomer B is (4-vinylphenyl) acetic acid represented by the formula (2). The proportion of the monomer unit corresponding to the vinyl monomer B in the copolymer of the present invention is, for example, 1 to 95% by weight, preferably 5 to 80% by weight, based on all monomer units constituting the copolymer. More preferably, it is 10 to 70% by weight. If this ratio is too small, the adhesion may be lowered, and if it is too much, the moisture absorption resistance may be lowered.

[Vinyl monomer C]
The copolymer of the present invention, in addition to the monomer unit corresponding to the vinyl monomer A represented by the formula (1) and the monomer unit corresponding to the vinyl monomer B represented by the formula (2), Furthermore, a monomer unit corresponding to the vinyl monomer C represented by the formula (3) may be included. In formula (3), R ² represents a hydrogen atom or a methyl group, and R ³ represents an organic group having 1 to 24 carbon atoms. a is an integer of 0 or 1; Vinyl monomer C does not include vinyl monomers A and B.

  Examples of the organic group include a hydrocarbon group which may have a substituent, a silicon atom-containing group, a heterocyclic group, a group in which two or more of these are bonded via one or more linking groups, and the like Is mentioned. Examples of the hydrocarbon group include an aliphatic hydrocarbon group such as an alkyl group, an alkenyl group, and an alkynyl group; an alicyclic hydrocarbon group such as a cycloalkyl group, a cycloalkenyl group, and a bridged carbocyclic group; an aromatic hydrocarbon group Is mentioned. Examples of the linking group include an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond (—CONH—), a urea bond, a urethane bond, and a carbonyl group (—CO—). , -NH-, a group in which two or more of these are bonded, and the like.

[Vinyl monomer having blocked isocyanate group]
As the vinyl monomer C represented by the formula (3), a compound in which R ³ is a group represented by the formula (4a), that is, a blocked isocyanate group (hereinafter sometimes referred to as a blocked isocyanate group). And vinyl monomers having a certain). In formula (4a), R ⁴ represents a C 1-8 divalent aliphatic saturated hydrocarbon group. R ⁵ represents a residue of an isocyanate group blocking agent R ⁵ H. The blocked isocyanate group is deblocked by heat to produce an active isocyanate group.

Examples of the divalent saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms in R ⁴ include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group. And a linear or branched divalent saturated aliphatic hydrocarbon group (alkylene group) such as an octamethylene group. Among these, C2-C4 bivalent saturated aliphatic hydrocarbon groups, such as ethylene group, trimethylene group, and propylene group, are preferable.

As the isocyanate group blocking agent R ⁵ H, blocking agents known to be used for blocking isocyanates, for example, phenol-based, lactam-based, active methylene-based, alcohol-based, mercaptan-based, acid amide-based, Any known blocking agent such as imide, amine, imidazole, urea, carbamate, imine, and oxime may be used. Examples of the isocyanate group blocking agent R ⁵ H include oxime blocking agents such as formaldoxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclohexanone oxime, diacetyl monooxime, and benzophenone oxime. A pyrazole block agent such as 3,5-dimethylpyrazole; an alcohol block agent such as methanol and ethanol; a phenol block agent such as phenol and cresol; a mercaptan block agent such as butyl mercaptan and hexyl mercaptan; an acetanilide and ε- Acid amide blocking agents such as caprolactam and γ-butyrolactam; active methylene blocking agents such as dimethyl malonate and methyl acetoacetate; succinimide, Imide-based blocking agents such as maleic imide; urea-based blocking agents; N-phenylcarbamic acid phenyl, 2-carbazolidone and other carbamic acid-based blocking agents; diphenylamine, aniline and other amine-based blocking agents; ethyleneimine, polyethyleneimine and the like Examples include imine blocking agents.

  As the isocyanate group blocking agent, a highly stable blocking agent which does not cause gelation in the production line of the curable resin composition is preferable. The deblocking temperature of the blocking agent is, for example, 100 to 300 ° C, preferably 150 to 250 ° C. Of the above blocking agents, oxime blocking agents and pyrazole blocking agents are preferred.

（式中、Ｒ⁹、Ｒ¹⁰は、同一又は異なって、炭素数１〜８のアルキル基を示す。Ｒ⁹及びＲ¹⁰は、互いに結合して、隣接する炭素原子とともに環を形成してもよい）
で表されるオキシム系ブロック剤が含まれる。 Particularly preferred blocking agents include the following formula (9)

(In the formula, R ⁹ and R ¹⁰ are the same or different and each represents an alkyl group having 1 to 8 carbon atoms. R ⁹ and R ¹⁰ may be bonded to each other to form a ring together with adjacent carbon atoms. Good)
The oxime block agent represented by these is included.

Examples of the alkyl group having 1 to 8 carbon atoms in R ⁹ and R ¹⁰ include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, Examples thereof include linear or branched alkyl groups such as hexyl group and octyl group. Among these, a linear or branched alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is preferable. Examples of the ring in which R ⁹ and R ¹⁰ are bonded to each other together with adjacent carbon atoms include, for example, about 3 to 12 membered (preferably 5 or 6 membered) cycloalkane such as cyclobutane ring, cyclopentane ring, cyclohexane ring and the like. A ring etc. are mentioned.

As a typical example of a vinyl monomer in which R ³ in formula (3) is a group represented by formula (4a), 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (= 2- (1-methylpropylideneaminooxycarbonylaminoethyl) methacrylate) [trade name “Karenz MOI-BM”, manufactured by Showa Denko KK, formula (10a) below], methacrylic acid 2- (3,5- And dimethylpyrazol-1-yl) carbonylaminoethyl [trade name “Karenz MOI-BP”, manufactured by Showa Denko KK, the following formula (10b)]. As for the deblocking temperature of the trade name “Karenz MOI-BM”, the 50% deblocking temperature is 130 ° C., and the 90% deblocking temperature is 150 ° C. Further, the deblocking temperature of the trade name “Karenz MOI-BP” is 50 ° C. deblocking temperature of 100 ° C. and 90% deblocking temperature of 120 ° C. As the vinyl monomer in which R ³ in the formula (3) is a group represented by the formula (4a), one or more selected from these can be used in combination.

In the copolymer of the present invention, deblocking of the monomer unit corresponding to the vinyl monomer in which R ³ in the formula (3) is a group represented by the formula (4a) is performed as shown in the following formula (11). proceed. The isocyanate group generated by this deblocking acts as a curable group. The isocyanate group mainly contributes to improvement of adhesion to the substrate.

The proportion of the monomer unit corresponding to the vinyl monomer in which R ³ in the formula (3) is a group represented by the formula (4a) is based on the total monomer units constituting the copolymer, For example, it is 1 to 95% by weight, preferably 5 to 80% by weight, and more preferably 10 to 70% by weight. If this ratio is too small, the adhesion may be lowered, and if it is too much, the solvent resistance may be lowered.

[Vinyl monomer having alkoxysilyl group]
Examples of the vinyl monomer C represented by the formula (3) include compounds in which R ³ is a group represented by the formula (4b), that is, an alkoxysilyl group-containing vinyl monomer. In the formula (4b), E represents a single bond or a divalent hydrocarbon group. R ⁶ and R ⁷ are the same or different and each represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. R ⁸ represents an alkyl group having 1 to 6 carbon atoms. b is an integer of 1 to 10 (preferably 1 to 5). Examples of the divalent hydrocarbon group represented by E include linear or branched alkylene such as methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group and hexamethylene group. Groups and the like. Among these, a C1-C3 linear or branched alkylene group such as a methylene group, an ethylene group, or a propylene group is particularly preferable.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁶ , R ⁷ and R ⁸ include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, Examples thereof include a linear or branched alkyl group such as a hexyl group. Among these, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group is preferable.

Examples of the alkoxy group having 1 to 6 carbon atoms represented by R ⁶ and R ⁷ include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, s-butoxy group, pentoxy group, hexyloxy And linear or branched alkoxy groups such as groups.

Examples of the vinyl monomer in which R ³ in the formula (3) is a group represented by the formula (4b) include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, γ -(Meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (Meth) acryloyloxypropyltriethoxysilane, β- (meth) acryloyloxyethyltrimethoxysilane, β- (meth) acryloyloxyethyltriethoxysilane, γ- (meth) acryloyloxybutylphenyldimethoxysilane, γ- (me ) Acryloyloxy-butylphenyl diethoxy silane alkoxysilyl group-containing polymerizable unsaturated compounds such as and the like. As a vinyl monomer whose R < ³ > in Formula (3) is group represented by Formula (4b), it can be used combining 1 type (s) or 2 or more types selected from these.

The proportion of the monomer unit corresponding to the vinyl monomer in which R ³ in the formula (3) is a group represented by the formula (4b) is based on the total monomer units constituting the copolymer, For example, it is 1 to 95% by weight, preferably 5 to 80% by weight, and more preferably 10 to 70% by weight. If this ratio is too small, the adhesion may be lowered, and if it is too much, the solvent resistance may be lowered, or the coating film becomes brittle and the adhesion may be lowered.

The vinyl monomer C represented by the formula (3) is a vinyl monomer in which R ³ in the formula (3) is a group represented by the formula (4a), and R ³ in the formula (3) is a formula. In addition to the vinyl monomer which is a group represented by (4b), for example, (meth) acrylic acid esters, aromatic vinyl compounds, hydroxyl group-containing monomers and the like can be mentioned. These monomers can be used alone or in combination of two or more.

［式中、Ｒ¹¹は水素原子又はメチル基を示し、Ｒ¹²は炭化水素基置換オキシ基を有していてもよい炭素数１〜１５（好ましくは、炭素数１〜１２）の炭化水素基を示す］ The (meth) acrylic acid ester is represented by the following formula (12).

[Wherein R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a hydrocarbon group having 1 to 15 carbon atoms (preferably 1 to 12 carbon atoms) optionally having a hydrocarbon group-substituted oxy group. Show]

Examples of the hydrocarbon group having 1 to 15 carbon atoms in R ¹² include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, Alkyl groups such as octyl group, 2-ethylhexyl group and decyl group; alicyclic hydrocarbon groups such as cyclohexyl group, dicyclopentanyl group and isobornyl group; aryl groups such as phenyl group; benzyl, 1-phenylethyl, 2 An aralkyl group such as a phenylethyl group; a group in which two or more of these are bonded.

Examples of the hydrocarbon group-substituted oxy group that the hydrocarbon group having 1 to 15 carbon atoms in R ¹² may have include an alkoxy group such as a methoxy group and an ethoxy group (for example, an alkoxy group having 1 to 10 carbon atoms). Group); aryloxy group such as phenoxy group; alicyclic hydrocarbon group-substituted oxy group such as cyclohexyloxy group and dicyclopentanyloxy group; carbon number 1 to 15 such as aralkyloxy group such as benzyloxy group (preferably Includes a hydrocarbon group-substituted oxy group having 1 to 12 carbon atoms.

  Representative examples of (meth) acrylic acid esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and phenylethyl (meth) acrylate.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, vinyl biphenyl, and the like.

  Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxy. Polyhydric alcohol and acrylic acid such as hexyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 8-hydroxyoctyl (meth) acrylate, 4-hydroxymethylcyclohexyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate, etc. Alternatively, a compound obtained by ring-opening polymerization of ε-caprolactone to a monoesterified product with methacrylic acid, or a monoesterified product of the above polyhydric alcohol with acrylic acid or methacrylic acid (product of Daicel Chemical Industries, Plaxel) A series, PLACCEL FM series, etc.), ethylene oxide, or propylene oxide ring-opening polymerization with hydroxyl group-containing compounds, and the like.

  In the present invention, the proportion of the monomer units corresponding to the vinyl monomer A and the total monomer units corresponding to the vinyl monomer B in the copolymer is, for example, , 20% by weight or more, preferably 30% by weight or more, and more preferably 40% by weight or more. If this ratio is too small, the solvent resistance and adhesion may not be sufficiently exhibited.

  The ratio of the monomer unit corresponding to vinyl monomer A, the monomer unit corresponding to vinyl monomer B, and the monomer unit corresponding to vinyl monomer C to the total copolymer is For example, it is 40% by weight or more, preferably 50% by weight or more, and more preferably 60% by weight or more based on all monomer units constituting the coalescence. If this ratio is too small, the solvent resistance and adhesion may not be sufficiently exhibited.

  In the copolymer of the present invention, the monomer unit corresponding to the vinyl monomer A, the monomer unit corresponding to the vinyl monomer B, and the vinyl monomer corresponding to C may each be one type. Well, two or more types may be present.

  The copolymer of the present invention may be composed only of a monomer unit corresponding to the vinyl monomer A and a monomer unit corresponding to the vinyl monomer B, but corresponds to the vinyl monomer C if necessary. The monomer unit corresponding to the monomer unit to be included may be included. In addition to the monomer unit corresponding to the vinyl monomer A, the monomer unit corresponding to the vinyl monomer B, the monomer unit corresponding to the vinyl monomer C, the monomer unit corresponding to another monomer is included. You may go out. The monomer unit corresponding to the other monomer is a monomer unit corresponding to a polymerizable monomer copolymerizable with vinyl monomer A and vinyl monomer B, and has solvent resistance and moisture absorption resistance. And if it is a structural unit which does not impair the adhesiveness with respect to the base material after a solvent resistance test, it will not specifically limit.

  The copolymer of the present invention can be obtained by vinyl polymerization of vinyl monomer A and vinyl monomer B, and if necessary, vinyl monomer C and other monomers. As the polymerization initiator used for the polymerization, known and commonly used radical initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvalero) Nitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2′-azobis (2-methylpropionate), 2,2-azobis (isobutyric acid) dimethyl , Azo compounds such as diethyl-2,2′-azobis (2-methylpropionate), dibutyl-2,2′-azobis (2-methylpropionate), benzoyl peroxide, lauroyl peroxide, t-butylperoxypi Examples thereof include barate, organic peroxides such as 1,1-bis (t-butylperoxy) cyclohexane, hydrogen peroxide, and the like. When a peroxide is used as a radical polymerization initiator, a redox initiator may be combined with a reducing agent. Of these, azo compounds are preferred, and in particular, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2-azobis (isobutyric acid) dimethyl are preferred. preferable.

  The amount of the polymerization initiator used can be appropriately selected within a range that does not impair smooth copolymerization, but is usually about 1 to 30% by weight, preferably based on the total amount of all monomer components and polymerization initiator. It is about 5 to 25% by weight.

  In the present invention, a chain transfer agent generally used in radical polymerization may be used in combination. Specific examples include thiols (such as n-dodecyl mercaptan, n-octyl mercaptan, n-butyl mercaptan, tert-butyl mercaptan, n-lauryl mercaptan, mercaptoethanol, mercaptopropanol, triethylene glycol dimercaptan). Mercaptopropionic acid, thiobenzoic acid, thioglycolic acid, thiomalic acid, etc.), alcohols (isopropyl alcohol, etc.), amines (dibutylamine, etc.), hypophosphites (sodium hypophosphite, etc.), α-methylstyrene dimer -, Terbinolene, myrcene, limonene, α-pinene, β-pinene and the like. The amount of the chain transfer agent is preferably 0.001 to 3% by weight with respect to the total amount of the radical polymerizable monomer. When using a chain transfer agent, it is preferable to mix with a polymerizable vinyl monomer in advance.

  In this invention, superposition | polymerization can be performed by the well-known and usual method used when manufacturing a styrene polymer and an acrylic polymer, such as solution polymerization, block polymerization, suspension polymerization, block-suspension polymerization, and emulsion polymerization. Among these, solution polymerization is preferable. Each monomer and polymerization initiator may be supplied all at once to the reaction system, or a part or all of them may be dropped into the reaction system. For example, a method in which a solution in which a polymerization initiator is dissolved in a polymerization solvent is dropped into a mixed solution of a monomer and a polymerization solvent kept at a constant temperature, or the monomer and the polymerization initiator are dissolved in the polymerization solvent in advance. A method in which the solution is dropped into a polymerization solvent maintained at a constant temperature for polymerization (drop polymerization method) can be employed.

The copolymer in the present invention is preferably copolymerized in a polymerization solvent. The polymerization solvent can be appropriately selected according to the monomer composition and the like. For example, ether (diethyl ether; ethylene glycol mono or dialkyl ether, diethylene glycol mono or dialkyl ether, propylene glycol mono or dialkyl ether, propylene glycol mono or diaryl ether, Propylene glycol mono or dialkyl ether, tripropylene glycol mono or dialkyl ether, 1,3-propanediol mono or dialkyl ether, 1,3-butanediol mono or dialkyl ether, 1,4-butanediol mono or dialkyl ether, glycerin mono , Chain ethers such as glycol ethers such as di- or trialkyl ethers; cyclic ethers such as tetrahydrofuran and dioxane), Ether (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, C _5-6 cycloalkane diol mono- or diacetate, C _5-6 cycloalkane Carboxylic acid esters such as methanol mono or diacetate; ethylene glycol monoalkyl ether acetate, ethylene glycol mono or diacetate, diethylene glycol monoalkyl ether acetate, diethylene glycol mono or diacetate, propylene glycol monoalkyl ether acetate, propylene glycol mono or di Acetate, dipropylene glycol monoalkyl ether acetate, dipropylene glycol mono or diacetate, 1,3-propanediol monoa Alkyl ether acetate, 1,3-propanediol mono- or diacetate, 1,3-butanediol monoalkyl ether acetate, 1,3-butanediol mono- or diacetate, 1,4-butanediol monoalkyl ether acetate, 1, Glycol acetate such as 4-butanediol mono or diacetate, glycerin mono, di or triacetate, glycerin mono or di _C1-4 alkyl ether di or monoacetate, tripropylene glycol monoalkyl ether acetate, tripropylene glycol mono or diacetate Or glycol ether acetates), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexene-1-o ), Amide (N, N-dimethylacetamide, N, N-dimethylformamide, etc.), sulfoxide (dimethylsulfoxide, etc.), alcohol (methanol, ethanol, propanol, C _5-6 cycloalkanediol, C _5-6 cyclo And alkanedimethanol), hydrocarbons (aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane), and mixed solvents thereof. The polymerization temperature can be appropriately selected within a range of about 30 to 150 ° C., for example.

  The copolymer in this invention is obtained by the said method. The weight average molecular weight of the copolymer is, for example, about 500 to 100,000, preferably 1000 to 40000, and more preferably about 2000 to 30000. If the weight average molecular weight is too small, the solvent resistance and adhesion may be lowered. If the weight average molecular weight is too large, the viscosity may be increased, and the copolymer may be difficult to handle.

  The polymerization solution obtained by the above-described method may be prepared by adjusting the solid content concentration, exchanging the solvent, or performing a filtration treatment, if necessary, followed by a curing catalyst [thermal acid generator ( Thermosetting catalyst, thermal cationic polymerization initiator), photoacid generator (photocuring catalyst, photocationic polymerization initiator)], photo radical initiator, curing agent, curing accelerator, additive (filler, antifoaming agent, By blending flame retardants, antioxidants, UV absorbers, colorants, stress reducing agents, flexibility-imparting agents, waxes, resins, cross-linking agents, halogen trapping agents, leveling agents, wetting improvers, etc.) A curable resin composition can be obtained. Moreover, the polymer produced | generated by superposition | polymerization is refine | purified by precipitation or the most precipitation, etc., The curable resin composition can also be obtained by melt | dissolving this refined polymer with the said appropriate additive in the solvent according to a use. .

  Among the curing catalysts, as the thermal acid generator, for example, Sun-Aid SI-45, Same as left SI-47, Same as left SI-60, Same as left SI-60L, Same as left SI-80, Same as left SI-80L, Same as left SI-100, Same as SI-100L, Same as left SI-145, Same as left SI-150, Same as left SI-160, Same as left SI-110L, Same as left SI-180L (above, Sanshin Chemical Co., Ltd., product name), CI-2921, CI-2920 CI-2946, CI-3128, CI-2624, CI-2638, CI-2064 (product of Nippon Soda Co., Ltd., product name), CP-66, CP-77 (product of Asahi Denka Kogyo Co., Ltd., product) Name), FC-520 (product of 3M, product name), diazonium salt, iodonium salt, sulfonium salt, phosphonium salt, selenium salt, oxonium salt Ammonium salts, and the like can be used.

  Examples of the photoacid generator include Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-950 (above, trade name of Union Carbide, USA), Irgacure 261 (Ciba Specialty Chemicals) Product name), SP-150, SP-151, SP-170, Optomer SP-171 (above, manufactured by Asahi Denka Kogyo Co., Ltd., product name), CG-24-61 (manufactured by Ciba Specialty Chemicals, Product name), DAICATII (manufactured by Daicel Chemical Industries, Ltd., product name), UVAC1591 (manufactured by Daicel-Cytec Co., Ltd., product name), CI-2064, CI-2639, CI-2624, CI-2481, CI-2734 , CI-2855, CI-2823, CI-2758 , Nippon Soda Co., Ltd., trade name), PI-2074 (Rhone-Poulenc, trade name, pentafluorophenyl borate toluylcumyl iodonium salt), FFC509 (3M product, trade name), BBI-102, BBI-101 , BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (trade name, manufactured by Midori Chemical Co., Ltd.), CD-1012 (trade name, manufactured by Sartomer, USA) ) And the like, and diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, oxonium salts, ammonium salts, and the like can be used.

  Examples of the photo radical initiator include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyldisulfite, orthobenzoylbenzoate. Methyl 4-ethylaminobenzoate (Nippon Kayaku Co., Ltd. Kayacure EPA), 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd. Kayacure DETX etc.), 2-methyl-1- [4- (methyl) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba-Gigi-Irgacure 907, etc.), tetra (t-butylperoxycarbonyl) benzophenone, benzyl, -Hydroxy-2-methyl-1-phenyl-propan-1-one, 4,4-bisdiethylaminobenzophenone, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl- 1,2′-biimidazole (B-CIM, etc., manufactured by Hodogaya Chemical Co., Ltd.) or the like can be used alone or in combination, and a photosensitizer can be added as necessary.

  The addition amount of the curing catalyst is, for example, 0.05 to 10% by weight, preferably 0.5 to 5% by weight with respect to the copolymer (resin component) in the curable resin composition. A curing catalyst can be used individually or in combination of 2 or more types. If the added amount is less than 0.05% by weight, there may be a problem that the performance as a curing catalyst is not exhibited. If the added amount exceeds 5% by weight, the curing catalyst remains, causing poor curing and resistance. There may be a problem that the solvent property is lowered.

  As a hardening | curing agent, a phenol resin, an acid anhydride, etc. are mentioned, for example. As the phenol resin, for example, a resin obtained by polymerizing phenol or cresol using formaldehyde can be used. This resin may be a copolymer of an alicyclic compound or aromatic compound such as dicyclopentadiene, naphthalene, or biphenyl. The addition amount of a phenol resin can be suitably selected, for example in the range of 0-200 weight part (for example, about 5-200 weight part) with respect to 100 weight part of copolymers of this invention.

Examples of the acid anhydride include polybasic acid anhydrides. Specifically, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, Δ ⁴ -tetrahydrophthalic anhydride, 4 -Methyl-Δ ⁴ -tetrahydrophthalic anhydride, 3-methyl-Δ ⁴ -tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, 4- (4-methyl-3-pentenyl) ) Tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, maleic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexene tetracarboxylic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, 4-methylhexahydro Phthalic anhydride, 3-methylhexahydrophthalic anhydride, vinyl ether-maleic anhydride Acid copolymers, alkyl styrene-maleic anhydride copolymer and the like. The compounding quantity of an acid anhydride can be suitably selected, for example in the range of 0-160 weight part (for example, about 20-160 weight part) with respect to 100 weight part of copolymers of this invention.

  When a phenol resin or acid anhydride is used as the curing agent, it is preferable to use a curing accelerator together. The curing accelerator is not particularly limited as long as it is generally used. However, phosphorus curing accelerators such as diazabicycloundecene curing accelerators (diazabicycloalkenes), phosphate esters, phosphines, Examples include amine-based curing accelerators such as tertiary amines and quaternary ammonium salts. Examples of the diazabicycloundecene-based curing accelerator include 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and salts thereof. In particular, 1,8-diazabicyclo [ 5.4.0] Organic salts of undecene-7 such as octylate, sulfonate, orthophthalate, and coalate are preferred. Specific examples of the other curing accelerator include tertiary amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol, 2-ethyl-4-methylimidazole, 1 -Phosphorus compounds (phosphonium salts, etc.) that do not contain aromatics, such as imidazoles such as cyanoethyl-2-ethyl-4-methylimidazole, tetra-n-butylphosphonium-O, O-diethyl phosphorodithioate, and tertiary amines Known compounds such as salts, metal salts such as quaternary ammonium salts and tin octylate can be exemplified. Furthermore, a metal organic acid salt can be used in combination with the organic acid salt of the diazabicycloalkenes. Examples of the metal organic acid salt include tin octylate, zinc octylate, tin naphthenate, and zinc naphthenate. The usage-amount of a hardening accelerator can be suitably selected in the range of 0-3 weight part (for example, about 0.05-3 weight part) with respect to 100 weight part of copolymers of this invention, for example.

  As said crosslinking agent, a polyfunctional alcohol compound, polyfunctional thiol compounds, etc. can be used, for example.

  The polyfunctional alcohol compound may be a compound having two or more hydroxyl groups. For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4- Multivalents such as butylene glycol, glycerin, diglycerin, D-glucose, D-glucitol, isoprene glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol Polyalkylene glycols such as alcohols, polyethylene glycols, polypropylene glycols, polybutylene glycols, polytetramethylene glycols, polycaprolactone diols, polycaprolacs Examples include tontriols and polycarbonate diols.

  The polyfunctional thiol compound may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglyco Rate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthio Glycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2, 4, -Trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine, tetraethylene glycol bis3-mercaptopropionate, trimethylolpropane tris3-mercaptopropionate , Tris (3-mercaptopropynyloxyethyl) isocyanurate, pentaerythritol tetrakis 3-mercaptopropionate, dipentaerythritol tetrakis 3-mercaptopropionate, 1,4-bis (3-mercaptobutyryloxy) butane, , 3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate), etc. Is mentioned. One type of polyfunctional alcohol compound or polyfunctional thiol compound may be used alone, or two or more types may be present.

  A radiation sensitive component can also be mix | blended with curable resin composition. As the radiation sensitive component, multifunctional such as multifunctional (meth) acrylate [including multifunctional urethane (meth) acrylate, multifunctional epoxy (meth) acrylate (type in which acrylic acid is added to epoxy group)] Examples thereof include epoxy compounds such as vinyl compounds and polyfunctional epoxy compounds, and epoxy resins. A polyfunctional (meth) acrylate and a heat or radiation polymerization initiator, or a polyfunctional epoxy compound and a heat or radiation acid generator may be combined. Each of these radiation-sensitive components, heat or radiation polymerization initiators, and heat or radiation acid generators may be used alone or in combination of two or more.

  Specific examples of polyfunctional (meth) acrylates include di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol, di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol, both ends Di (meth) acrylates of both end hydroxylated polymers such as hydroxypolybutadiene, both end hydroxypolyisoprene and both end hydroxypolycaprilactone, glycerin, 1,2,4, -butanetriol, trimethylolalkane, tetramethylolalkane , Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as pentaerythritol, dipentaerythritol, poly (polyalkylene glycol adducts of trihydric or higher polyhydric alcohols ( ) Acrylates, poly (meth) acrylates of cyclic polyols such as 1,4-cyclohexanediol, 1,4-benzenediols, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, Examples thereof include oligo (meth) acrylates such as alkyd resin (meth) acrylate, silicon resin (meth) acrylate, and spirane resin (meth) acrylate. These may be used alone or in combination of two or more.

  As the multifunctional epoxy compound, for example, the trade name “Celoxide 2021”, the trade name “Celoxide 2081”, the trade name “Celoxide 3000”, the trade name “EHPE3150”, the trade name “Epolide GT401” (above, Daicel Chemical Industries Ltd.) Company name), trade name "Epolite 4000" (manufactured by Kyoeisha Chemical Co., Ltd.) and the like. These may be used alone or in combination of two or more.

  The curable resin composition may contain fine particles such as glass fine particles, metal oxide fine particles, rubber fine particles, and ceramic fine particles. Fine particles such as fine particles, metal oxide fine particles, rubber fine particles, and ceramic fine particles may be blended. Moreover, you may mix | blend glass fiber, a fiber fiber, and a Kepla fiber. These can be used alone or in combination of two or more.

  The curable resin composition thus obtained can obtain a cured product (cured film or the like) having excellent solvent resistance and moisture absorption resistance and high adhesion even when touched by the solvent. Therefore, it is useful as a paint, a coating agent, an adhesive, and the like, and can be suitably used particularly in the field of electronic materials.

  By curing the curable resin composition, a cured product having excellent physical properties can be obtained. For example, the curable resin composition is applied to various substrates or substrates by a method such as a spin coater or a slit coater to form a coating film, and then a cured product is obtained by curing the coating film. Can do. Examples of the base material or substrate include glass, ceramic, silicon wafer, metal, and plastic. Coating with a spin coater, slit coater, or the like can be performed by a known method.

  Curing of the coating film is performed by heating, irradiating and irradiating active energy rays, or heating after exposure. When the curable resin composition is cured by heat, the heating temperature is in the range of 50 ° C to 260 ° C, preferably in the range of 80 ° C to 240 ° C. When the curable resin composition is cured by light, light of various wavelengths, for example, ultraviolet rays, X-rays, g-rays, i-rays, excimer lasers, etc. are used for exposure. Although the thickness of the coating film after hardening can be suitably selected according to a use, generally it is 0.1-40 micrometers, Preferably it is 0.3-20 micrometers, More preferably, it is about 0.5-10 micrometers.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the weight average molecular weight (polystyrene conversion) and dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) of the produced | generated copolymer were measured on condition of the following.
Device: Detector: RID-10A (Shimadzu Corporation)
Pump: LC-10ADVP (Shimadzu Corporation)
System controller: SCL-10AVP (Shimadzu Corporation)
Degasser: DGU-14A (Shimadzu Corporation)
Autoinjector: SIL-10AF (Shimadzu Corporation)
Column: Waters Styragel HR3, Styragel HR4, Styragel HR5, 3 in total Mobile phase: THF (tetrahydrofuran)
Flow rate: 1mL / min
Temperature: Oven (40 ° C), RI (40 ° C)
Detector: RI POLARITY (+)
Injection volume: 50μL

Example 1
An appropriate amount of nitrogen was flowed into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, 30 parts by weight of 4-vinylphenethyloxirane was added, and the mixture was heated to 80 ° C. with stirring. Next, a solution prepared by dissolving 70 parts by weight of (4-vinylphenyl) acetic acid in 10 parts by weight of methoxybutyl acetate (manufactured by Daicel Chemical Industries) was dropped into the flask over about 4 hours using a dropping pump. On the other hand, a solution prepared by dissolving 0.9 parts by weight of a polymerization initiator 2,2′-azobisisobutyronitrile in 40 parts by weight of methoxybutyl acetate was dropped into the flask using another dropping pump over about 4 hours. . After completion of dropping of the polymerization initiator, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a copolymer solution having a solid content of 50% by weight. The produced copolymer had a weight average molecular weight Mw of 14,000 and a dispersity of 2.10.

Example 2
A copolymer having a solid content of 42% by weight, except that the monomer composition is changed to 50 parts by weight of 4-vinylbenzyloxirane and 50 parts by weight of (4-vinylphenyl) acetic acid. A solution was obtained. The produced copolymer had a weight average molecular weight Mw of 18000 and a dispersity of 1.80.

Example 3
The same procedure as in Example 1 was performed except that the monomer composition was changed to 35 parts by weight of 4-vinylbenzyloxirane, 35 parts by weight of 4-vinylphenethyloxirane, and 30 parts by weight of (4-vinylphenyl) acetic acid. A copolymer solution having a solid content of 55% by weight was obtained. The produced copolymer had a weight average molecular weight Mw of 18000 and a dispersity of 2.20.

Example 4
The monomer composition is 30 parts by weight of 4-vinylbenzyloxirane, 40 parts by weight of (4-vinylphenyl) acetic acid, 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (trade name “ Except for changing to 30 parts by weight of “Karenz MOI-BM” (manufactured by Showa Denko KK), a copolymer solution having a solid content of 49% by weight was obtained in the same manner as in Example 1. The produced copolymer had a weight average molecular weight Mw of 13,000 and a dispersity of 2.00.

Example 5
The monomer composition is 30 parts by weight of 4-vinylphenethyloxirane, 40 parts by weight of (4-vinylphenyl) acetic acid, 30 parts by weight of γ-methacryloxypropyltriethoxysilane (trade name SZ6063, manufactured by Toray Dow Corning Co., Ltd.). A copolymer solution having a solid content of 45% was obtained in the same manner as in Example 1 except that the copolymer solution was changed to. The produced copolymer had a weight average molecular weight Mw of 26000 and a dispersity of 2.80.

Example 6
The monomer composition is 30 parts by weight of 4-vinylbenzyloxirane, 40 parts by weight of (4-vinylphenyl) acetic acid, 2-O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (trade name “Karenz “MOI-BM” (manufactured by Showa Denko KK) 15 parts by weight, γ-methacryloxypropyltriethoxysilane (manufactured by Toray Dow Corning Co., Ltd., trade name SZ6063) 15 parts by weight Thus, a copolymer solution having a solid content of 47% by weight was obtained. The resulting copolymer had a weight average molecular weight Mw of 19000 and a dispersity of 2.30.

Comparative Example 1
Except changing the monomer composition to only 100 parts by weight of 4-vinylbenzyloxirane, the same operation as in Example 1 was performed to obtain a copolymer solution having a solid content of 40% by weight. The produced copolymer had a weight average molecular weight Mw of 18000 and a dispersity of 1.70.

Comparative Example 2
Except for changing the monomer composition to only 100 parts by weight of 4-vinylphenethyloxirane, the same operation as in Example 1 was performed to obtain a copolymer solution having a solid content of 42% by weight. The produced copolymer had a weight average molecular weight Mw of 24,000 and a dispersity of 1.80.

Comparative Example 3
Except for changing the monomer composition to 50 parts by weight of glycidyl methacrylate and 50 parts by weight of (4-vinylphenyl) acetic acid, the same operation as in Example 1 was carried out to obtain a copolymer solution having a solid content of 54% by weight. Obtained. The resulting copolymer had a weight average molecular weight Mw of 19000 and a dispersity of 2.10.

Comparative Example 4
Except for changing the monomer composition to 3,4-epoxycyclohexylmethyl methacrylate (trade name “Cyclomer M100”, manufactured by Daicel Chemical Industries, Ltd.) and 50 parts by weight of (4-vinylphenyl) acetic acid. The same operation as in Example 1 was performed to obtain a copolymer solution having a solid content of 51% by weight. The produced copolymer had a weight average molecular weight Mw of 22000 and a dispersity of 2.25.

Comparative Example 5
Except changing the monomer composition to 70 parts by weight of 4-vinylphenethyloxirane and 30 parts by weight of methacrylic acid, the same operation as in Example 1 was performed to obtain a copolymer solution having a solid content of 54% by weight. The produced copolymer had a weight average molecular weight Mw of 20000 and a dispersity of 2.10.

Evaluation test (1) Preparation of test piece for evaluation After applying the copolymer solution (curable resin composition) obtained in each Example and Comparative Example to a base material with a spin coater, on a hot plate at 80 ° C. After heating for 10 minutes, each evaluation test piece was produced by heating in an oven at 230 ° C. for 60 minutes. A glass plate and a stainless steel plate were used as the base material.

(2) Solvent resistance In Examples and Comparative Examples, isopropyl alcohol (IPA), methyl ethyl ketone (MEK), and N-methyl pyrrolidone (NMP) were dropped on each of the test pieces prepared with glass plates, Left for 10 minutes. After washing with water, if the location where the solvent has been dripped has not changed at all ◎, a trace of the solvent will remain, but if it disappears if wiped off, ○ will leave a trace of the solvent and will not disappear even if wiped off. △, if it was completely discolored, x. Similar results were obtained when using test specimens made of stainless steel plates.

(3) Adhesion (after solvent resistance test)
In the examples and comparative examples, the adhesiveness was measured by peeling from the substrate in accordance with JIS K-5600-5-6 for the places where the solvent resistance test was performed. Moreover, according to the classification | category prescribed | regulated by the classification | category of JIS K-5600-5-6 8.3 Table 1 test result, it evaluated about the glass plate and the stainless steel plate based on the following reference | standard.
A: The test result classification was “0”.
○: It was “1” in the classification of the test results.
Δ: “2” in the classification of test results.
X: “3” and “4” in the classification of the test results.

(4) Hygroscopic resistance In the examples and comparative examples, the test specimens made of glass plates were cured for 24 hours in a constant temperature and humidity chamber at a temperature of 20 ° C./humidity of 65%, and the coating film was then treated with TG / DTA. It was measured by (differential thermothermal gravimetric simultaneous measurement device).
The temperature when the 1% weight loss was 200 ° C. or higher was evaluated as “◯”, the temperature between 100 ° C. and 200 ° C. as “Δ”, and the temperature at 100 ° C. or lower as “X”.

  The results of the evaluation test are shown in Table 1.

Abbreviations in Table 1 represent the following.
DN-1: 4-vinylbenzyloxirane DN-2: 4-vinylphenethyloxirane GMA: glycidyl methacrylate cyclomer M100: 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel Chemical Industries, Ltd.)
CMSCA: (4-vinylphenyl) acetic acid MOI-BM: 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (manufactured by Showa Denko KK)
SZ6030: γ-methacryloxypropyltrimethoxysilane (manufactured by Dow Corning Toray)

  As is apparent from the table, the cured coating films obtained from the curable resin compositions of the examples were excellent in both solvent resistance, adhesion to the substrate after the solvent resistance test, and moisture absorption resistance. . On the other hand, the cured coating film obtained from the curable resin composition of the comparative example was inferior in any respect.

Claims (9)

Following formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group, and X represents a divalent hydrocarbon group having 1 to 6 carbon atoms)
A monomer unit corresponding to the vinyl monomer A represented by the following formula (2):

A copolymer containing at least a monomer unit corresponding to the vinyl monomer B represented by Further, the following formula (3)

(Wherein R ² represents a hydrogen atom or a methyl group, R ³ represents an organic group having 1 to 24 carbon atoms, a is an integer of 0 or 1)
The copolymer of Claim 1 containing the monomer unit corresponding to the vinyl monomer C represented by these. R ³ in the above formula (3) is the following formula (4a)

(Wherein, R ⁴ represents a divalent aliphatic saturated hydrocarbon to a group .R ⁵ is the residue of a blocking agent R ⁵ H isocyanate groups of 1 to 8 carbon atoms)
The copolymer of Claim 2 which is group represented by these. R ³ in the above formula (3) is the following formula (4b)

(In formula, E shows a single bond or a bivalent hydrocarbon group. R < ⁶ > and R < ⁷ > are the same or different, and show a C1-C6 alkyl group or a C1-C6 alkoxy group. R ⁸ represents an alkyl group having 1 to 6 carbon atoms, and b is an integer of 1 to 10)
The copolymer of Claim 2 which is group represented by these.   A curable resin composition in which a light and / or thermal polymerization initiator is blended with the copolymer according to any one of claims 1 to 4.   Furthermore, the curable resin composition of Claim 5 in which the polyfunctional vinyl compound is mix | blended.   Furthermore, the curable resin composition of Claim 5 in which the polyfunctional thiol compound is mix | blended.   Furthermore, the curable resin composition of Claim 5 with which the epoxy compound and / or the epoxy resin are mix | blended.   Hardened | cured material obtained by hardening | curing the curable resin composition in any one of Claims 5-8.