JP2009221275A - Photocurable and/or thermosetting copolymer, curable resin composition and cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable copolymer which excels in synthesis stability and storage stability, has good curing properties, and enables both epoxy crosslinking and radical crosslinking. <P>SOLUTION: The photocurable and/or thermosetting copolymer has a polymerizable unsaturated group in the side chain and is obtained by the addition reaction of an epoxy group of an epoxy group-containing polymerizable unsaturated compound (d) to part of carboxyl groups of a copolymer (P) comprising at least a monomer unit (A) corresponding to a carboxyl group-containing polymerizable unsaturated compound (a), a monomer unit (B) corresponding to a bridged alicyclic group-containing polymerizable unsaturated compound (b) having an epoxy group on the ring, and a monomer unit (C) corresponding to a bridged alicyclic group-containing polymerizable unsaturated compound (c) having a double bond in the ring. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a light and / or thermosetting copolymer having a carboxyl group, an epoxy group and a polymerizable unsaturated group in the side chain, and a curable resin composition containing the light and / or thermosetting copolymer. And a cured product obtained by curing the curable resin composition. The light and / or thermosetting copolymer and a curable resin composition containing the same are a soda resist for a printed wiring board, a resist for an optical waveguide, a liquid resist, a dry film, a photo spacer used for a liquid crystal display, It is useful as a material for forming an overcoat, a color resist, a black matrix, an insulating film, and the like.

  In general, in the field of manufacturing various electronic devices that require fine processing on the order of submicrons, such as VLSI, there is an increasing demand for higher density and higher integration of devices. For this reason, the request | requirement with respect to the photolithographic technique which is a fine pattern formation method is becoming severer. On the other hand, in electronic components such as liquid crystal display elements, integrated circuit elements, solid-state imaging elements, protective films for preventing deterioration and damage, interlayer insulating films provided for insulating between wirings arranged in layers, A flattening film for flattening the element surface, an insulating film for maintaining electrical insulation, and the like are provided. In particular, in the case of a liquid crystal display element, for example, in a TFT type liquid crystal display element, a polarizing plate is provided on a glass substrate, a transparent conductive circuit layer such as ITO and a thin film transistor (TFT) are formed, and covered with an interlayer insulating film. On the other hand, a polarizing plate is provided on the glass plate, a black matrix layer and a color filter layer pattern are formed as necessary, and a transparent conductive circuit layer and an interlayer insulating film are sequentially formed as a top plate. The back plate and the top plate are made to face each other through a spacer and liquid crystal is sealed between the two plates. The photosensitive resin composition used there is transparent, heat resistant, developable and It is required to have excellent flatness.

  As a method for increasing the sensitivity of a resist, a chemically amplified resist using a photoacid generator as a photosensitizer is well known. For example, using a resin composition containing a resin containing a structural unit having an epoxy group and a photoacid generator, a protonic acid is generated from the photoacid generator by exposure, and the epoxy group is cleaved to cause a crosslinking reaction. As a result, the resin becomes insoluble in the developer and a pattern is formed. Further, the resist is moved in the resist solid phase by the heat treatment after the exposure, and the chemical change of the resist resin or the like is amplified catalytically by the acid. . In this way, a dramatic increase in sensitivity has been achieved as compared with conventional resists having a photoreaction efficiency (reaction per photon) of less than 1. Currently, most of the resists that are developed are chemically amplified, and the use of a chemical amplification mechanism is indispensable for the development of high-sensitivity materials that can cope with shorter wavelengths of exposure light sources.

  On the other hand, the insulating film provided in the TFT type liquid crystal display element or the integrated circuit element needs to be finely processed. Therefore, as a material for forming the insulating film, a radiation-sensitive resin composition is generally used. Such a radiation-sensitive resin composition is required to have high radiation sensitivity in order to obtain high productivity. In addition, when the insulating film has low solvent resistance, the insulating film is swelled, deformed, peeled off from the substrate, etc. by an organic solvent, which is serious in the production of liquid crystal display elements and integrated circuit elements. Trouble occurs. Therefore, such an insulating film is required to have excellent solvent resistance. Furthermore, high transparency is required for an insulating film provided in a liquid crystal display element, a solid-state imaging element, or the like as necessary.

  A vinyl copolymer resin having an epoxy group and a carboxyl group in the side chain has been proposed as a curable resin used for various applications described above and having excellent storage stability and curing characteristics (Patent Document 1, etc.). . Since this curable resin has an epoxy group in the side chain, it can be crosslinked (epoxy crosslinked) with a crosslinking agent having a functional group reactive to the epoxy group. On the other hand, as a curable resin used for various applications, a vinyl copolymer resin having a carboxyl group in a side chain and an epoxy compound having a polymerizable unsaturated group in part of the carboxyl group has been proposed. (Patent Document 2 etc.). Since this curable resin has a polymerizable unsaturated group in the side chain, radical crosslinking using a radical initiator is possible.

  However, conventionally, few vinyl copolymer resins obtained by adding an epoxy compound having an epoxy group and a carboxyl group in the side chain and having a polymerizable unsaturated group in a part of the carboxyl group are known. This is because, when a vinyl polymer having an epoxy group and a carboxyl group in the side chain is reacted with an epoxy compound having a polymerizable unsaturated group, generally the epoxy group originally present in the vinyl polymer is converted into a carboxyl in the vinyl polymer. This is because it reacts with the group to increase the gelation or the viscosity of the resin solution during the reaction, and the desired curable resin cannot be obtained.

JP 2006-193718 A JP 2000-191737 A

An object of the present invention is to provide a curable copolymer having excellent synthesis stability and storage stability, good curing characteristics, and capable of both epoxy crosslinking and radical crosslinking, and curable properties containing the curable copolymer. The object is to provide a resin composition and a cured product obtained by curing the curable resin composition.
Another object of the present invention is to provide a curable resin composition that is excellent in heat resistance and solvent resistance and that can obtain a cured product having high hardness, and a cured product obtained by curing it.

As a result of intensive studies to achieve the above object, the present inventors have a carboxyl group-containing polymerizable unsaturated compound and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring. Part of a copolymer obtained by polymerizing a polymerizable unsaturated compound and a polymerizable unsaturated compound having a dicyclopentene ring (tricyclo [5.2.1.0 ^2,6 ] -3-decene ring) When an epoxy group of an epoxy group-containing polymerizable unsaturated compound is added to the carboxyl group of the copolymer, the internal addition reaction between the epoxy group and the carboxyl group in the copolymer hardly proceeds, and the carboxyl group in the copolymer And an epoxy group of an epoxy group-containing polymerizable unsaturated compound proceed to have a carboxyl group in the molecule, and an epoxy group capable of epoxy crosslinking and a polymerizable unsaturated group capable of radical crosslinking Can be easily obtained without gelation during the reaction, the curable copolymer is excellent in storage stability, and the curable copolymer containing the curable copolymer is cured. It has been found that when a curable composition is cured by light or heat, a cured product having excellent heat resistance and solvent resistance and high hardness can be obtained. The present invention has been completed based on these findings.

（式中、Ｒ^aは、それぞれ、水素原子又はヒドロキシル基を有していてもよい炭素数１〜４のアルキル基を示し、Ｒ^bは、それぞれ、単結合又はヘテロ原子を含んでいてもよい炭素数１〜１８のアルキレン基を示す）
で表される化合物から選択される少なくとも１種の環上にエポキシ基を有する有橋脂環式基含有重合性不飽和化合物（ｂ）に対応するモノマー単位（Ｂ）、及び下記式（３）及び（４）

（式中、Ｒ^cは、それぞれ、水素原子又はヒドロキシル基を有していてもよい炭素数１〜４のアルキル基を示し、Ｒ^dは、それぞれ、単結合又はヘテロ原子を含んでいてもよい炭素数１〜１８のアルキレン基を示す）
で表される化合物から選択される少なくとも１種の環内に二重結合を有する有橋脂環式基含有重合性不飽和化合物（ｃ）に対応するモノマー単位（Ｃ）を少なくとも含む共重合体（Ｐ）の一部のカルボキシル基に、エポキシ基含有重合性不飽和化合物（ｄ）のエポキシ基を付加反応させて得られる、側鎖に重合性不飽和基を有する光及び／又は熱硬化性共重合体を提供する。 That is, the present invention relates to a monomer unit (A) corresponding to the carboxyl group-containing polymerizable unsaturated compound (a), the following formulas (1) and (2).

(In the formula, each R ^a represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, and each R ^b may contain a single bond or a hetero atom. An alkylene group having 1 to 18 carbon atoms)
A monomer unit (B) corresponding to the bridged alicyclic group-containing polymerizable unsaturated compound (b) having an epoxy group on at least one ring selected from the compounds represented by formula (2), and the following formula (3): And (4)

(In the formula, each R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, and each R ^d may contain a single bond or a hetero atom, respectively. An alkylene group having 1 to 18 carbon atoms)
A copolymer comprising at least a monomer unit (C) corresponding to a bridged alicyclic group-containing polymerizable unsaturated compound (c) having a double bond in at least one ring selected from the compounds represented by Light and / or thermosetting having a polymerizable unsaturated group in the side chain obtained by addition reaction of an epoxy group of the epoxy group-containing polymerizable unsaturated compound (d) with a part of the carboxyl groups of (P) A copolymer is provided.

  The copolymer (P) may further contain another monomer unit (E) in addition to the monomer unit (A), the monomer unit (B) and the monomer unit (C).

［式中、Ｒ¹は水素原子又は炭素数１〜７のアルキル基を示し、Ｒ²は炭素数１〜１８の直鎖状又は分岐鎖状アルキル基、炭素数２〜１８のアルケニル基、アリール基、アラルキル基、−（Ｒ³−Ｏ）_m−Ｒ⁴基（式中、Ｒ³は炭素数１〜１２の２価の炭化水素基、Ｒ⁴は水素原子又は炭化水素基、ｍは１以上の整数を示す）、又は非芳香族性の単環もしくは多環構造を含む基を示す］
で表される不飽和カルボン酸エステル（ｅ２）、及び下記式（６）

（Ｒ⁵は置換基を有していてもよいフェニル基、置換基を有していてもよいアラルキル基、又は置換基を有していてもよいシクロアルキル基を示す）
で表されるＮ−置換マレイミド（ｅ３）からなる単量体群より選択される少なくとも１種の重合性不飽和化合物に対応するモノマー単位が好ましい。 As the monomer unit (E), styrene (e1) optionally substituted with an alkyl group or a hydroxyl group, the following formula (5)

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, R ² represents a linear or branched alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, aryl Group, aralkyl group, — (R ³ —O) _m —R ⁴ group (wherein R ³ is a divalent hydrocarbon group having 1 to 12 carbon atoms, R ⁴ is a hydrogen atom or a hydrocarbon group, and m is 1) Or a group containing a non-aromatic monocyclic or polycyclic structure]
An unsaturated carboxylic acid ester (e2) represented by the following formula (6)

(R ⁵ represents a phenyl group which may have a substituent, an aralkyl group which may have a substituent, or a cycloalkyl group which may have a substituent)
A monomer unit corresponding to at least one polymerizable unsaturated compound selected from the monomer group consisting of N-substituted maleimides (e3) represented by

  The present invention also provides a curable resin composition containing the light and / or thermosetting copolymer.

  This curable resin composition may further contain a curing agent and / or a curing catalyst.

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

The curable copolymer of the present invention is excellent in synthesis stability and storage stability, has good curing characteristics, and is capable of both epoxy crosslinking and radical crosslinking.
According to the curable resin composition of the present invention, a cured product having excellent heat resistance and solvent resistance and high hardness can be obtained by curing. This cured product is also excellent in alkali resistance and solvent resistance. Therefore, it is useful for applications such as soda resist for printed wiring boards, resist for optical waveguides, liquid resists, dry films, photo spacers used for liquid crystal displays, overcoats, color resists, black matrices, and insulating films.

The light and / or thermosetting copolymer of the present invention comprises a monomer unit (A) corresponding to the carboxyl group-containing polymerizable unsaturated compound (a), a compound represented by the above formulas (1) and (2). The monomer unit (B) corresponding to the bridged alicyclic group-containing polymerizable unsaturated compound (b) having an epoxy group on at least one selected ring, and represented by the above formulas (3) and (4) A copolymer (P) containing at least a monomer unit (C) corresponding to the bridged alicyclic group-containing polymerizable unsaturated compound (c) having a double bond in at least one ring selected from Is a copolymer having a polymerizable unsaturated group in the side chain obtained by addition reaction of the epoxy group of the epoxy group-containing polymerizable unsaturated compound (d) with a part of the carboxyl groups. The copolymer (P) contains a specific epoxy group-containing ring structure called 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring in the molecule, and this epoxy group is a polymer. Since it is difficult to react with the carboxyl group therein, the addition reaction between a part of the carboxyl groups in the copolymer (P) and the epoxy group-containing polymerizable unsaturated compound (d) proceeds smoothly and gels. And can be easily synthesized. In addition, since it has a carboxyl group in the molecule, it exhibits an alkali-soluble function that dissolves in an alkali developer, and since it has an epoxy group and a polymerizable unsaturated group in the molecule, both epoxy crosslinking and radical crosslinking are possible. It has excellent curing properties. Furthermore, in the monomer unit (C), since the double bond in the ring of the bridged alicyclic group is involved in the polymerization, higher hardness, solvent resistance and heat resistance are imparted to the cured film.

[Carboxyl group-containing polymerizable unsaturated compound (a)]
As the carboxyl group-containing polymerizable unsaturated compound (a), a monocarboxylic acid having a polymerizable unsaturated group, a dicarboxylic acid having a polymerizable unsaturated group, or the like can be used. Examples of the carboxyl group-containing polymerizable unsaturated compound include aliphatic unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; and aliphatic unsaturated monocarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. Saturated dicarboxylic acid; modified unsaturated carboxylic acid in which the chain between the unsaturated group such as β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid and the carboxyl group is extended, etc. Is mentioned. Further, as a carboxyl group-containing polymerizable unsaturated compound, a compound obtained by lactone modification of (meth) acrylic acid, for example, a compound represented by the following formula (7), a hydroxyalkyl ester of (meth) acrylic acid is lactone modified, A compound obtained by acid-modifying the terminal hydroxyl group with an acid anhydride, for example, a compound represented by the following formula (8), a compound obtained by acid-modifying the terminal hydroxyl group of a polyether polyol ester of (meth) acrylic acid, for example, A compound represented by the following formula (9) can also be used.

In the formula (7), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, a methyl group or an ethyl group, a represents an integer of 4 to 8, and b represents An integer of 1 to 10 is shown. The a R ⁷ and R ⁸ may be the same or different.

In formula (8), R ⁹ represents a hydrogen atom or a methyl group, R ¹⁰ and R ¹¹ are the same or different and represent a hydrogen atom, a methyl group or an ethyl group, c is an integer of 4 to 8, and d is An integer of 1 to 10 is shown. R ¹² may have a divalent aliphatic saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic saturated or unsaturated hydrocarbon group having 3 to 6 carbon atoms, or a substituent. A good divalent arylene group is shown. The c R ¹⁰ and R ¹¹ may be the same or different.

In Formula (9), R ¹³ represents a hydrogen atom or a methyl group, R ¹⁴ and R ¹⁵ are the same or different and represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group, and e represents 1 to 1 The integer of 10 and f show the integer of 1-10. R ¹⁶ may have a divalent aliphatic saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic saturated or unsaturated hydrocarbon group having 3 to 6 carbon atoms, or a substituent. A good divalent arylene group is shown. Each of e R ¹⁴ and R ¹⁵ may be the same or different.

  Examples of the divalent aliphatic saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms include methylene, ethylene, ethylidene, propylene, isopropylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene and decamethylene. And vinylene groups. Examples of the divalent alicyclic saturated or unsaturated hydrocarbon group having 3 to 6 carbon atoms include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylidene, and cyclohexylidene groups. It is done. Examples of the divalent arylene group that may have a substituent include phenylene, tolylene, and xylylene groups.

  As the carboxyl group-containing polymerizable unsaturated compound (a), in particular, (meth) acrylic acid, maleic anhydride, at least one compound selected from the compounds represented by formulas (7) to (9) [among others] , A compound represented by formula (7)], at least one compound selected from (meth) acrylic acid and compounds represented by formulas (7) to (9) [in particular, represented by formula (7) In combination with the compound].

[Bridged alicyclic group-containing polymerizable unsaturated compound (b) having an epoxy group on the ring]
In the bridged alicyclic-containing polymerizable unsaturated compound (b) having an epoxy group on at least one ring selected from the compounds represented by the formulas (1) and (2), the formula (1), R ^{a in} (2) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, and R ^b may contain a single bond or a hetero atom, respectively. A good alkylene group having 1 to 18 carbon atoms is shown.

  Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl group and the like. Examples of the alkyl group having 1 to 4 carbon atoms having a hydroxyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyisopropyl, Examples include 2-hydroxyisopropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl group and the like.

Ra is preferably ^a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and particularly preferably a hydrogen atom or a methyl group.

In the alkylene group having 1 to 18 carbon atoms which may contain a hetero atom in R ^b, the hetero atom may be bonded to the terminal of the alkylene group or may be interposed between carbon atoms constituting the alkylene group. Good. Examples of the hetero atom include nitrogen, oxygen, sulfur atom and the like.

（式中、Ｒ^eは炭素数１〜１８のアルキレン基を示し、ｎは０以上の整数を示す。但し、式中の全炭素数は０〜１８である）
で表される基が挙げられる。 As a representative example of R ^b , the following formula (10)

(Wherein, R ^e represents an alkylene group having 1 to 18 carbon atoms, n represents represents an integer of 0 or more. However, the total number of carbons in the formula is 0 to 18)
The group represented by these is mentioned.

The alkylene group having 1 to 12 carbon atoms in R ^e, e.g., methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene methylene, octadecamethylene group Etc. As R ^e , an alkylene group having 1 to 12 carbon atoms (particularly 1 to 6 carbon atoms) such as methylene, ethylene, propylene, tetramethylene and hexamethylene groups is particularly preferable. n is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, particularly preferably 0 or 1.

Other typical examples of R ^b include alkylene groups having 1 to 18 carbon atoms such as methylene group, ethylene group, propylene group and trimethylene group [especially alkylene having 1 to 12 carbon atoms (particularly 1 to 6 carbon atoms). Group]; a thioalkylene group having 1 to 18 carbon atoms such as a thiomethylene group, a thioethylene group, and a thiopropylene group [particularly, a thioalkylene group having 1 to 12 carbon atoms (particularly 1 to 6 carbon atoms)]; Examples thereof include aminoalkylene groups having 1 to 18 carbon atoms such as ethylene group and aminopropylene group [particularly, aminoalkylene groups having 1 to 12 carbon atoms (particularly 1 to 6 carbon atoms)].

R ^b is preferably a single bond [when n is 0 in the above formula (10)], an alkylene group having 1 to 6 carbon atoms (particularly 1 to 3 carbon atoms), 1 to 6 carbon atoms ( In particular, an oxyalkylene group having 2 to 3 carbon atoms [in the above formula (10), n is 1 and R ^e is a C _1-6 alkylene group (particularly a C _2-3 alkylene group)], and more Preferably, it is a single bond or an oxyethylene group.

Bridged alicyclic group-containing polymerizable unsaturated compound having an epoxy group on the ring represented by formulas (1) and (2) (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] As a typical example of a decane ring-containing compound), an epoxidized dicyclopentenyl (meth) acrylate represented by the following formula (11) [= 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] decan-9-yl (meth) acrylate; 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate], represented by the following formula (12) Epoxidized dicyclopentenyloxyethyl (meth) acrylate [= 2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yloxy) ethyl (meth) acrylate; (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Decan-8-yloxy) ethyl (meth) acrylate], epoxidized dicyclopentenyloxybutyl (meth) acrylate represented by the following formula (13), epoxidized dicyclopentenyloxy represented by the following formula (14) Examples include hexyl (meth) acrylate. Of these, epoxidized dicyclopentenyl (meth) acrylate and epoxidized dicyclopentenyloxyethyl (meth) acrylate are particularly preferred. In the following formula, R ^{a ′} represents a hydrogen atom or a methyl group.

式（１）で表される化合物と式（２）で表される化合物は、それぞれ単独で用いることができる。また、それらは任意の割合で混合して用いることができる。両者を混合して用いる場合、その割合は、好ましくは、式（１）：式（２）＝５：９５〜９５：５、より好ましくは１０：９０〜９０：１０、さらに好ましくは２０：８０〜８０：２０である。

The compound represented by the formula (1) and the compound represented by the formula (2) can be used alone. Moreover, they can be mixed and used in arbitrary ratios. When both are used in combination, the ratio is preferably the formula (1): formula (2) = 5: 95 to 95: 5, more preferably 10:90 to 90:10, still more preferably 20:80. ~ 80: 20.

[Bridged alicyclic group-containing polymerizable unsaturated compound (c) having a double bond in the ring]
In the bridged alicyclic group-containing polymerizable unsaturated compound (c) having a double bond in at least one ring selected from the compounds represented by the formulas (3) and (4), the formula (3) ) (R ^c is in 4), respectively, a hydrogen atom or a hydroxyl group or an alkyl group having 1 to 4 carbon atoms which may have a, R ^d are each, include a single bond or a hetero atom The C1-C18 alkylene group which may be mentioned is shown.

Examples of the alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group in R ^c include the same as the alkyl group having 1 to 4 carbon atoms which may have ^a hydroxyl group in ^Ra . It is done. .

R ^c is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and particularly preferably a hydrogen atom or a methyl group.

The alkylene group having 1 to 18 carbon atoms which may contain a hetero atom in R ^d, the same as the alkylene group having 1 to 18 carbon atoms which may contain a hetero atom in the R ^b. A typical example of R ^{d is} the same as a typical example of R ^b .

R ^d is preferably a single bond, an alkylene group having 1 to 6 carbon atoms (particularly 1 to 3 carbon atoms), an oxyalkylene group having 1 to 6 carbon atoms (particularly 2 to 3 carbon atoms), More preferably, it is a single bond or an oxyethylene group.

Bridged alicyclic group-containing polymerizable unsaturated compound having a double bond in the ring represented by formulas (3) and (4) (tricyclo [5.2.1.0 ^2,6 ] -3-decene As a typical example of the ring-containing compound), dicyclopentenyl (meth) acrylate represented by the following formula (15) [= tricyclo [5.2.1.0 ^2,6 ] -3-decen-9-yl (Meth) acrylate; tricyclo [5.2.1.0 ^2,6 ] -3-decen-8-yl (meth) acrylate], dicyclopentenyloxyethyl (meth) acrylate represented by the following formula (16) [= 2- (tricyclo [5.2.1.0 ^2,6 ] -3-decene-9-yloxy) ethyl (meth) acrylate; 2- (tricyclo [5.2.1.0 ^2,6 ]- 3-decen-8-yloxy) ethyl (meth) acrylate], represented by the following formula (17) Examples thereof include dicyclopentenyloxybutyl (meth) acrylate represented by dicyclopentenyloxyhexyl (meth) acrylate represented by the following formula (18). Of these, dicyclopentenyl (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate are particularly preferable. In the following formula, R ^{a ′} represents a hydrogen atom or a methyl group.

  The compound represented by Formula (3) and the compound represented by Formula (4) can be used alone. Moreover, they can be mixed and used in arbitrary ratios. When both are used in combination, the ratio is preferably the formula (3): formula (4) = 5: 95 to 95: 5, more preferably 10:90 to 90:10, still more preferably 20:80. ~ 80: 20.

[Other polymerizable unsaturated compounds (e)]
The copolymer (P) may further have another monomer unit (E) in addition to the monomer unit (A), the monomer unit (B) and the monomer unit (C). As such other monomer units (E), styrene (e1) optionally substituted with an alkyl group or a hydroxyl group, unsaturated carboxylic acid ester (e2) represented by the above formula (5), and the above formula And monomer units corresponding to at least one polymerizable unsaturated compound selected from the monomer group consisting of N-substituted maleimides (e3) represented by (6).

  Examples of styrene (e1) that may be substituted with an alkyl group or a hydroxyl group include styrene, α-methylstyrene, vinyl toluene, and hydroxystyrene.

In the unsaturated carboxylic acid ester (e2) represented by the formula (5), in the formula (5), R ¹ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, and R ² represents 1 to 18 carbon atoms. A linear or branched alkyl group, an alkenyl group having 2 to 18 carbon atoms, an aryl group, an aralkyl group, a — (R ³ —O) _m —R ⁴ group (wherein R ³ has 1 to 12 carbon atoms) A divalent hydrocarbon group, R ⁴ represents a hydrogen atom or a hydrocarbon group, m represents an integer of 1 or more, or a group containing a non-aromatic monocyclic or polycyclic structure.

The alkyl group having 1 to 7 carbon atoms in R ^1, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t- butyl, and hexyl groups. R ¹ is particularly preferably a hydrogen atom or a methyl group.

Examples of the linear or branched alkyl group having 1 to 18 carbon atoms in R ² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, octyl, decyl, dodecyl group and the like. It is done. Examples of the alkenyl group having 2 to 18 carbon atoms include vinyl, allyl, 3-butenyl, 5-hexenyl group and the like. Examples of the aryl group include phenyl, naphthyl, and tolyl groups. Examples of the aralkyl group include aralkyl groups having about 7 to 18 carbon atoms such as benzyl, 1-phenylethyl, 2-phenylethyl, trityl, and 3-phenylpropyl groups.

In R ² - in (R ³ -O) _m -R ⁴ group, R ³ is a divalent hydrocarbon group having 1 to 12 carbon atoms, R ⁴ represents a hydrogen atom or a hydrocarbon group, m is 1 or more Indicates an integer. Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms in R ³ include 2 to 12 carbon atoms (particularly 2 to 6) such as ethylidene, ethylene, isopropylidene, trimethylene, propylene, tetramethylene, and hexamethylene groups. ) Linear or branched alkylene group; 3-6 membered divalent alicyclic hydrocarbon group such as cyclohexylene, cyclohexylidene group and the like. Examples of the hydrocarbon group for R ⁴ include aliphatic hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and hexyl groups (eg, C _1-10 alkyl groups); cyclopentyl groups and cyclohexyl groups. Alicyclic carbonization such as bridged carbocyclic groups such as cycloalkyl groups, norbornyl groups (bicyclo [2.2.1] heptyl group) and tricyclo [5.2.1.0 ^2,6 ] decyl groups Examples thereof include a hydrogen group; an aryl group such as phenyl and naphthyl group; and a divalent group in which two or more of these are bonded. m is preferably an integer of 1 to 20, more preferably an integer of 1 to 4, and particularly preferably 1.

The group containing a non-aromatic monocyclic or polycyclic structure in R ² includes a group having an alicyclic hydrocarbon skeleton. Examples of the group having an alicyclic hydrocarbon skeleton include the following formula (19)
-X ¹ -R ¹⁷ (19)
(Wherein R ¹⁷ represents an alicyclic hydrocarbon group, and X ¹ represents a single bond or a linking group)
The group represented by these is mentioned.

The alicyclic hydrocarbon group for R ¹⁷ may have, for example, a substituent such as an alkyl group having 1 to 6 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, or a trimethylcyclohexyl group. -15-membered cycloalkyl group, other monocyclic alicyclic hydrocarbon group; bicyclo [2.2.1] heptan-2-yl group (= norbornan-2-yl group), isobornyl group, tricyclo [5 .2.1.0 ^2,6 ] decan-9-yl group, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, tricyclo [4.4.0.1 ^2,5 ] Undecan-3-yl group, tricyclo [4.4.0.1 ^2,5 ] undecan-4-yl group, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecan-3-yl group, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] a polycyclic group having about 6 to 20 carbon atoms which may have a substituent such as an alkyl group having 1 to 6 carbon atoms such as dodecan-4-yl group and adamantan-1-yl group. An alicyclic hydrocarbon group (bridged cyclic hydrocarbon group) is mentioned. Among these, a polycyclic alicyclic hydrocarbon group (bridged hydrocarbon group) having about 6 to 20 carbon atoms which may have a substituent such as an alkyl group having 1 to 6 carbon atoms. preferable.

Examples of the linking group for X ¹ include a linear or branched chain having about 1 to 12 carbon atoms (particularly 1 to 6) such as methylene, ethylidene, ethylene, isopropylidene, trimethylene, propylene, tetramethylene, and hexamethylene groups. An alkylene group; a 3- to 6-membered divalent alicyclic hydrocarbon group such as cyclohexylene or cyclohexylidene group; a divalent aromatic hydrocarbon group having about 6 to 15 carbon atoms such as a phenylene group; Oxygen atom (ether bond); sulfur atom (thioether bond); -NH-; carbonyl group (-CO-); a divalent group in which two or more of these are bonded (for example, -CH ₂ CH ₂ O-, -CH _{2 CH 2 CH 2 CH 2 O -} , - such as _{CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 O- and the like oxyalkylene group) and the like. X ¹ is preferably a single bond, a linear or branched alkylene group having 1 to 6 carbon atoms, an oxyalkylene group, or a group in which two or more oxyalkylene groups are bonded.

The group containing a non-aromatic monocyclic or polycyclic structure in R ² includes a lactone ring-containing group. As the lactone ring-containing group, for example, the following formula (20)
-X ² -R ¹⁸ (20)
(Wherein R ¹⁸ represents a cyclic group containing a lactone ring, and X ² represents a single bond or a linking group)
The group represented by these is mentioned.

As the cyclic group containing a lactone ring in R ¹⁸ , for example, a monocyclic ring having only a 5- to 15-membered (particularly 5- or 6-membered) lactone ring such as a γ-butyrolactone ring, a δ-valerolactone ring, and an ε-caprolactone ring A norbornanelactone ring (= 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one ring), 6-oxabicyclo [3.2.1] octane-7 -On ring, 8-oxabicyclo [4.3.0 ^1,6 ] nonan-7-one ring, 4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one ring, etc. 5 to 15-membered (especially 5- or 6-membered) lactone ring and alicyclic ring are condensed polycyclic cyclic groups. Examples of the linking group for X ² include the same as the linking group for X ¹ .

The group containing a non-aromatic monocyclic or polycyclic structure in R ² includes a cyclic ether skeleton-containing group (a group containing a 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring. Is excluded). As the cyclic ether skeleton-containing group, for example, the following formula (21)
-X ³ -R ¹⁹ (21)
(Wherein R ¹⁹ represents a cyclic group containing a cyclic ether skeleton, and X ³ represents a single bond or a linking group)
The group represented by these is mentioned.

Examples of the cyclic group containing a cyclic ether skeleton in R ¹⁹ include oxiranyl group (epoxy group), 2-methyl-2-oxiranyl group, 3-methyl-2-oxiranyl group, oxetanyl group, 3-methyl-3- Cyclic groups consisting only of 3- to 8-membered cyclic ether skeletons such as oxetanyl group, 3-ethyl-3-oxetanyl group, tetrahydrofuranyl group and tetrahydropyranyl group; 3 to 8 members such as 3,4-epoxycyclohexyl group And a monocyclic (especially oxirane ring) having only a cyclic ether skeleton and a monocyclic or polycyclic alicyclic ring are condensed. Examples of the linking group for X ³ include the same as the linking group for X ¹ . The polymerizable unsaturated compound having a cyclic ether skeleton-containing group is used in such a range that gelation does not occur.

Representative examples of the unsaturated carboxylic acid ester represented by the formula (5) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, C _1-18 alkyl (meth) acrylates such as hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate; Aralkyl (meth) acrylates such as benzyl (meth) acrylate; (Meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Alkyl or aryl-substituted oxypolyalkylene glycols such as coal (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, and methoxytriethylene glycol (meth) acrylate ( (Meth) acrylate; (meth) acrylic acid aryloxyalkyl ester such as 2-phenyloxyethyl (meth) acrylate; trimethylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, 2- (tricyclo [5. .1.0 ^2,6] decan-9-yloxy) ethyl (meth) acrylate, 2- (tricyclo [5.2.1.0 ^2,6] decan-8-yloxy) ethyl (meth) acrylate, 4- (Tricyclo [5.2.1.0 ^2,6 ] decan-9-yloxy) butyl (meth) acrylate, 4- (Tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) butyl ( (Meth) acrylate, 6- (tricyclo [5.2.1.0 ^2,6 ] decan-9-yloxy) hexyl (meth) acrylate, 4- (tricyclo [5.2.1.0 ^2,6 ] decane- (Meth) acrylic acid esters containing alicyclic carbon rings such as 8-yloxy) hexyl (meth) acrylate and adamantyl (meth) acrylate; γ-butyrolactone-2-yl (meth) acrylate, γ-butyrolacto (Meth) acrylic acid ester containing a lactone ring such as -3-yl (meth) acrylate, γ-butyrolactone-4-yl (meth) acrylate, norbornane lactone (meth) acrylate; glycidyl (meth) acrylate, oxetanyl (meth) (Meth) acrylic acid ester containing a cyclic ether skeleton such as acrylate, 3-methyl-3-oxetanyl (meth) acrylate, 3-ethyl-3-oxetanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate [formula (1 And the compound represented by (2)].

Among the unsaturated carboxylic acid esters represented by the formula (5), in particular, C _1-4 alkyl (meth) acrylate, aralkyl (meth) acrylate, (meth) acrylic acid hydroxyalkyl ester [(meth) acrylic acid hydroxy C _2-6 alkyl ester and the like] are preferable.

In the N-substituted maleimide (e3) represented by the formula (6), R ⁵ in the formula (6) is a phenyl group which may have a substituent, and an aralkyl group which may have a substituent. Or a cycloalkyl group which may have a substituent. Examples of the substituent include a C _1-4 alkyl group such as a methyl group, a C _1-4 alkoxy group such as a methoxy group, a hydroxyl group, and a carboxyl group. Examples of the phenyl group that may have a substituent include phenyl, naphthyl, and tolyl groups. Examples of the aralkyl group which may have a substituent include benzyl, p-methylbenzyl, 2-phenylethyl group and the like. Examples of the cycloalkyl group which may have a substituent include 3- to 8-membered cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl groups.

  As typical examples of the N-substituted maleimide represented by the formula (6), for example, N-cycloalkylmaleimide such as N-cyclopentylmaleimide, N-cyclohexylmaleimide and N-cyclooctylmaleimide; N-phenylmaleimide and the like N-arylmaleimide; N-aralkylmaleimide such as N-benzylmaleimide and the like.

  Copolymer (P) is a monomer unit (E) other than the monomer unit (A), monomer unit (B), and monomer unit (C), and is an unsaturated dicarboxylic acid diester such as dimethyl maleate; acrylonitrile, It may contain monomer units corresponding to polymerizable unsaturated compounds other than the above, such as methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene and the like.

  In the present invention, the proportion of each monomer unit in the copolymer (P) can be appropriately selected according to the application and desired properties. The proportion of the monomer unit (A) in the copolymer (P) is, for example, 1 to 80% by weight, preferably 2 to 70% by weight, more preferably 5 to 60% by weight, based on all monomer units constituting the polymer. %. The proportion of the monomer unit (B) in the copolymer is, for example, about 5 to 95% by weight, preferably about 10 to 90% by weight, and more preferably about 20 to 80% by weight with respect to all the monomer units constituting the polymer. is there. The proportion of the monomer units (C) in the copolymer is, for example, 0.5 to 30% by weight, preferably 1 to 20% by weight, more preferably 1 to 10% by weight, based on all monomer units constituting the polymer. Degree. The proportion of the monomer unit (E) in the copolymer is usually 0 to 70% by weight (for example 1 to 70% by weight), preferably 0 to 50% by weight (for example, based on all monomer units constituting the polymer). For example, it is about 3 to 50% by weight), more preferably about 0 to 40% by weight (for example, 5 to 40% by weight). If the ratio of each monomer unit is within the above range, the copolymer synthesis stability, the storage stability of the composition containing the copolymer, the developability when used as a radiation-sensitive resin, and the solvent resistance of the cured film Property, heat resistance, etching resistance, hardness, transparency and the like are extremely good.

  The copolymer of the present invention includes the carboxyl group or acid anhydride group-containing polymerizable unsaturated compound (a), a bridged alicyclic group-containing polymerizable unsaturated compound (b) having an epoxy group on the ring, A monomer mixture comprising a bridged alicyclic group-containing polymerizable unsaturated compound (c) having a double bond in the ring and other polymerizable unsaturated compound (e) used as necessary is copolymerized. It can manufacture by attaching | subjecting to.

  As a polymerization initiator used for copolymerization, a normal radical polymerization initiator can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis (2-methylpropionate), diethyl-2,2'-azobis (2-methylpro) Pionate), azo compounds such as dibutyl-2,2'-azobis (2-methylpropionate), benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1-bis (t-butylperoxy) cyclohexane And organic peroxides such as hydrogen peroxide. 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), dimethyl-2,2'-azobis (2- Methyl propionate) is preferred.

  The amount of the polymerization initiator used can be appropriately selected within a range that does not impair smooth copolymerization, but is usually about 0.5 to 20% by weight based on the total amount of monomers (total monomer components) and polymerization initiator. Preferably, it is about 1 to 15% by weight.

  The copolymerization can be performed by a conventional method used for producing a styrene polymer or an acrylic polymer, such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, and emulsion polymerization. Among these, solution polymerization is preferable. The monomer and the 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 polymerization solvent can be appropriately selected according to the monomer composition and the like. As a polymerization solvent, for example, ether (diethyl ether; 3-methoxy-1-butanol, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, chain ethers such as glycol ethers such as tripropylene glycol n-butyl ether, propylene glycol phenyl ether, and cyclic ethers such as tetrahydrofuran and dioxane). Esters (methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, ethyl lactate acetate , Methyl lactate acetate, cyclohexanol acetate, furfuryl alcohol acetate, ethyl-3-ethoxypropionate, 2-acetoxy-2-methylmalonic acid dimethyl ester; 3-methoxybutyl acetate, propylene glycol diacetate, 1,6- Glycol diesters such as hexanediol diacetate, 1,3-butanediol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, Glycol ether esters), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), amides (N, N-dimethylacetate, etc.) Amide, N, N-dimethylformamide, etc.), sulfoxide (dimethylsulfoxide, etc.), alcohol (methanol, ethanol, propanol, etc.), hydrocarbon (aromatic hydrocarbons such as benzene, toluene, xylene, etc., aliphatic hydrocarbons such as hexane, etc. And alicyclic hydrocarbons such as cyclohexane), lactones (such as γ-butyrolactone), and mixed solvents thereof. The polymerization temperature can be appropriately selected within a range of about 30 to 150 ° C., for example.

  A copolymer (P) is produced by the above method. The weight average molecular weight of the copolymer (P) is, for example, 2000 to 50000, preferably 3500 to 40000, and more preferably about 4000 to 30000. The degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of the copolymer (P) is, for example, 1 to 3, and preferably about 1 to 2.5.

  The acid value of the copolymer (P) is, for example, 20 to 500 mgKOH / g, preferably 50 to 300 mgKOH / g.

  The copolymer (P) can be isolated by a known method such as reprecipitation and subjected to the next addition reaction, but the polymerization solution is used as it is or after being subjected to treatment such as concentration, dilution, solvent substitution, etc. You may use for the next addition reaction.

[Epoxy group-containing polymerizable unsaturated compound (d)]
The epoxy group-containing polymerizable unsaturated compound (d) to be subjected to addition reaction with a part of the carboxyl groups of the copolymer (P) is a compound having a radical polymerizable unsaturated group and an epoxy group in the molecule. For example, a polymerizable unsaturated compound having a glycidyl group and a polymerizable unsaturated compound having an alicyclic epoxy group are exemplified. The epoxy group-containing polymerizable unsaturated compound (d) can be used alone or in combination of two or more.

  Examples of the polymerizable unsaturated compound having a glycidyl group include glycidyl methacrylate, β-methyl glycidyl methacrylate, allyl glycidyl ether, 2-hydroxyethyl acrylate glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, and the like. Examples of the polymerizable unsaturated compound having an alicyclic epoxy group include the following compounds (d-1) to (d-11).

In the above formula, R ^f represents a hydrogen atom or a methyl group, R ^g represents an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include linear or branched alkylene groups such as methylene, ethylidene, ethylene, isopropylidene, trimethylene, propylene, tetramethylene, and hexamethylene groups.

  Although the compounds represented by the above formulas (1) and (2) can be used as the epoxy group-containing polymerizable unsaturated compound (d), since the addition reaction rate is slow, the epoxy group-containing polymerizable unsaturated compound (d) ), It is preferable to use an epoxy group-containing polymerizable unsaturated compound other than the compounds represented by the formulas (1) and (2).

[Light and / or thermosetting copolymer]
The light and / or thermosetting copolymer having a polymerizable unsaturated group in the side chain of the present invention (sometimes simply referred to as “the curable copolymer of the present invention”) is the copolymer (P ) Is partly reacted with an epoxy group of the epoxy group-containing polymerizable unsaturated compound (d).

  The addition amount when the epoxy group of the epoxy group-containing polymerizable unsaturated compound (d) undergoes addition reaction with a part of the carboxyl groups of the copolymer (P) is based on the total amount of carboxyl groups of the copolymer (P). For example, it is preferably in the range of 5 to 95 mol% (particularly 20 to 80 mol%). When the addition amount is less than 5 mol%, the curability (active energy ray curability, thermosetting, etc.) of the resulting copolymer is lowered, and the physical properties of the cured film tend to be lowered. On the other hand, when the addition amount exceeds 95 mol%, the addition reaction takes time and the synthesis stability tends to be lowered.

  In the addition reaction between a part of the carboxyl groups of the copolymer (P) and the epoxy groups of the epoxy group-containing polymerizable unsaturated compound (d), it is preferable to use a catalyst. Examples of the catalyst include tertiary amines such as dimethylbenzylamine, triethylamine, tetramethylethylenediamine, tri-n-octylamine, and 1,8-diazabicyclo [5.4.0] undecene-7 (DBU); Quaternary ammonium salts such as ammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide; alkylureas such as tetramethylurea; alkylguanidines such as tetramethylguanidine; metal compounds such as cobalt naphthenate (metal salts etc.); organic metals Complexes: Phosphine compounds such as triphenylphosphine (particularly tertiary phosphine). These catalysts can be used alone or in combination of two or more.

  The amount of the catalyst used varies depending on the type of catalyst, but is usually 0.01 to 30% by weight, preferably 0.1 to 25% by weight, based on the epoxy group-containing polymerizable unsaturated compound (d). More preferably, it is about 1 to 20% by weight. If this catalyst remains, it may cause problems when the produced curable copolymer is used. Therefore, the catalyst is deactivated (inactive) by a known method at an appropriate time after the addition reaction. Or may be removed.

  The addition reaction is usually performed in the presence of a solvent. The solvent is not particularly limited as long as it dissolves the raw material, and for example, the solvent exemplified as the polymerization solvent can be used. Other solvents may be used as the solvent.

  The reaction temperature during the addition reaction is, for example, about 10 to 150 ° C, preferably about 60 to 100 ° C. In the addition reaction, a polymerization inhibitor may be added to the system in order to suppress gelation due to polymerization of the polymerizable unsaturated group. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, phenothiazine and the like. For the same reason, the addition reaction is preferably performed in an oxygen atmosphere. The oxygen concentration should be a concentration that does not form an explosive mixture in the reaction system, and is usually adjusted to 1 to 9%.

  The acid value of the curable copolymer of the present invention obtained by the above addition reaction is, for example, in the range of 10 to 350 mgKOH / g, preferably 20 to 200 mgKOH / g. When the acid value is less than 10 mgKOH, the solubility in an alkaline developer is lowered and the developability tends to be lowered. Conversely, when it exceeds 350 mgKOH / g, the water resistance and electrical properties of the cured film are liable to be lowered. The double bond equivalent [weight of resin per mole of unsaturated groups (g)] of the curable polymer of the present invention is, for example, about 300 to 4000, preferably about 500 to 2000. If the double bond equivalent is too low, curing shrinkage tends to occur, and if it is too high, the coating strength after curing tends to decrease.

  The weight average molecular weight of the curable copolymer of this invention is 2000-100000, for example, Preferably it is 3500-70000, More preferably, it is about 4000-50000. When the weight average molecular weight is too small, tack-free performance and moisture resistance of the coating film after exposure are lowered, film slippage is liable to occur during development, and resolution is also liable to be lowered. On the other hand, if the weight average molecular weight is too large, developability and storage stability tend to decrease. The dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the curable copolymer of the present invention is, for example, about 1 to 3, preferably about 1 to 2.5.

  Although the curable copolymer of the present invention can be isolated by a known method such as reprecipitation and used for the preparation of a curable resin composition, the reaction solution after the addition reaction is used as it is, or diluted, concentrated, and solvent. You may use what gave processes, such as replacement | exchange and filtration, for preparation of curable resin composition.

The curable copolymer of the present invention contains, in the molecule, a carboxyl group derived from a carboxyl group-containing polymerizable unsaturated compound (a) (a carboxyl group that does not undergo an addition reaction), formula (1) and / or ( 2) an epoxy group-containing ring structure called 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring derived from the epoxy group-containing polymerizable unsaturated compound (b) A dicyclopentene ring (tricyclo [5.2.1] derived from a bridged alicyclic group-containing polymerizable unsaturated compound (c) having a double bond in the ring represented by (3) and / or (4). has .0 ^2,6] -3-ring structure having decene ring) endocyclic double bond of the polymerizable unsaturated group derived from the epoxy-containing polymerizable unsaturated compound (d) . When used as a resist resin, for example, the carboxyl group functions as an alkali-soluble group that dissolves in an alkali developer. Moreover, it can function also as a crosslinking point which reacts with the crosslinking agent which has reactivity with respect to a carboxyl group. The epoxy group functions as a crosslinking point that reacts with a crosslinking agent having reactivity with the epoxy group (for example, by cationic polymerization). Furthermore, the double bond in the ring and the polymerizable unsaturated group function as a crosslinking point that reacts with a crosslinking agent having radical reactivity, and the hardness, solvent resistance, and heat resistance of a cured product (cured film, etc.). Contributes to the improvement of sex. As described above, since the curable copolymer of the present invention has a plurality of functional groups having different functions and reaction characteristics in the molecule, a carboxyl group and an epoxy group are used depending on the use and desired cured product characteristics. By appropriately selecting the ratio of double bond in the ring and polymerizable unsaturated group, a cured product having a wide range of physical properties can be obtained and can be used for various applications.

[Curable resin composition]
The curable resin composition of the present invention contains the curable copolymer of the present invention. Other components are added to the curable resin composition of the present invention depending on the application. Other components include, for example, a solvent, a curing agent or curing catalyst for curing (crosslinking) an epoxy group, a photopolymerization initiator for polymerizing a polymerizable unsaturated group, a radical reactive diluent (diluting monomer or Oligomer).

  The content of the curable copolymer of the present invention in the curable resin composition is, for example, 5 to 95% by weight, preferably 10 to 90% by weight, based on the total amount excluding the solvent in the curable resin composition. More preferably, it is about 30 to 90% by weight (particularly 50 to 90% by weight).

  As the solvent, in addition to the solvents exemplified as the polymerization solvent, various solvents according to the application can be used. Of these, esters, ketones and ethers are preferred. A solvent can be used individually or in combination of 2 or more types. The content of the solvent is preferably 60 to 90% by weight, more preferably about 70 to 85% by weight with respect to the entire curable resin composition from the viewpoint of applicability and the like.

  As a hardening | curing agent, an epoxy resin, a phenol resin, an acid anhydride etc. are mentioned, for example.

  The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule (polyfunctional epoxy resin). For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type Examples thereof include epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, glycidyl ether type epoxy resins such as brominated bisphenol A, dimer acid diglycidyl esters, and phthalic acid diglycidyl esters. Moreover, a polyfunctional alicyclic epoxy resin can also be used as an epoxy resin. An epoxy resin can be used individually or in combination of 2 or more types. The compounding quantity of an epoxy resin can be suitably selected, for example in the range of 0-50 weight part (for example, about 5-50 weight part) with respect to 100 weight part of curable copolymers of this invention.

  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 curable copolymers of this invention. In addition, the phenolic resin is used in such an amount that the phenolic hydroxyl group is 0 to 1.8 mol (for example, about 0.1 to 1.8 mol) with respect to 1 mol of the epoxy group of the curable copolymer of the present invention. May be.

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 curable copolymers of this invention. Moreover, even if it uses acid anhydride of the quantity which will be 0-1.3 equivalent (for example, about 0.2-1.3 equivalent) with respect to 1 equivalent of epoxy groups of the curable copolymer of this invention. Good.

  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 and 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, for example in the range of 0-3 weight part (for example, about 0.05-3 weight part) with respect to 100 weight part of curable copolymers of this invention.

  Examples of the curing catalyst include a thermal cationic polymerization initiator and a photo cationic polymerization initiator. These can be used alone or in combination of two or more. The thermal cationic polymerization initiator is a component that releases a substance that initiates cationic polymerization by heating. Examples of the thermal cationic polymerization initiator include aryldiazonium salts [for example, PP-33 [manufactured by Asahi Denka Kogyo Co., Ltd.]], aryliodonium salts, arylsulfonium salts [for example, FC-509, FC-520 [or more, Manufactured by 3M Co., Ltd.], UVE1014 [G. E. Manufactured by Co., Ltd.], CP-66, CP-77 [above, manufactured by Asahi Denka Kogyo Co., Ltd.], SI-60L, SI-80L, SI-100L, SI-110L [above, Sanshin Chemical Industry Co., Ltd. Manufactured]], allene-ion complex [for example, CG-24-61 [manufactured by Ciba Geigy Co., Ltd.]] and the like. Furthermore, the system of the chelate compound of metals, such as aluminum and titanium, and an acetoacetate ester or diketones, and silanol or phenols is also included. Examples of the chelate compound include aluminum trisacetylacetonate and aluminum trisacetoacetate ethyl. Examples of silanols or phenols include compounds having silanols such as triphenylsilanol and compounds having acidic hydroxyl groups such as bisphenol S. The compounding quantity of a thermal cationic polymerization initiator is 0-20 weight part (for example, about 0.01-20 weight part) with respect to 100 weight part of curable copolymers of this invention.

  The cationic photopolymerization initiator is a component that releases a substance that initiates cationic polymerization by irradiation with active energy rays such as ultraviolet rays. Examples of the photocationic polymerization initiator include hexafluoroantimonate salt, pentafluorohydroxyantimonate salt, hexafluorophosphate salt, hexafluoroarzate salt and the like. The compounding quantity of a photocationic polymerization initiator is 0-20 weight part (for example, about 0.01-20 weight part) with respect to 100 weight part of curable copolymers of this invention.

  The photopolymerization initiator for polymerizing a polymerizable unsaturated group or the like in the copolymer of the present invention is not particularly limited, but acetophenone-based [diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl Propan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzyldimethyl ketal, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, etc.], benzophenone, benzoin, thioxanthone Biimidazole, oxime, triazine, acylphosphine oxide polymerization initiators, and the like are preferable. Among these, acetophenone polymerization initiators are particularly preferable.

  A photopolymerization initiation assistant can be used together with the photopolymerization initiator. Examples of photopolymerization initiators include amine-based photopolymerization initiators such as methyl 4-dimethylaminobenzoate and 4,4′-bis (diethylamino) benzophenone; phenylthioacetic acid, methylphenylthioacetic acid, dimethylphenylthioacetic acid And aromatic heteroacetic acid photopolymerization initiation assistants such as phenoxyacetic acid and naphthoxyacetic acid.

  The blending amount of the photopolymerization initiator is, for example, about 0.1 to 40 parts by weight, preferably about 1 to 30 parts by weight with respect to 100 parts by weight of the total amount of the copolymer of the present invention and the radical reactive diluent described later. is there.

  Examples of radical reactive diluents (diluted monomers or oligomers) include aliphatic alcohols such as isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, or (meth) acrylic acid esters of alicyclic alcohols. Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate; ethylene glycol mono- or di (meth) acrylate, methoxyethylene glycol mono- or di (meth) acrylate, tetramethylene Glycol mono or di (meth) acrylates such as glycol mono or di (meth) acrylate, tripropylene glycol mono or di (meth) acrylate; 3,4-epoxycyclohexylmethyl (Meth) acrylate, epoxy group-containing (meth) acrylate such as glycidyl (meth) acrylate; glycerin di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri- or tetra (meth) acrylate, dipentaerythritol hexa ( Examples thereof include polyols such as (meth) acrylate or (meth) acrylates of adducts thereof with alkylene oxide. The polyfunctional radically reactive diluent functions as a crosslinking agent. A radical reactive diluent can be used individually or in combination of 2 or more types.

  The compounding amount of the radical reactive diluent is, for example, 1 to 70% by weight, preferably 5 to 60% by weight, and more preferably 15 to 15% by weight based on the total amount of the curable copolymer and the radical reactive diluent of the present invention. It is about 55% by weight.

  The curable resin composition may also include other resins, polyols, photosensitizers, photoacid generators, fillers, colorants, pigment dispersants, antioxidants, depending on the application and desired properties. UV absorbers, anti-aggregating agents, aggregating agents, chain transfer agents, adhesion-imparting agents, leveling agents, and the like may be blended.

  The curable resin composition can be prepared by mixing the curable copolymer of the present invention and the other components, stirring uniformly, and filtering as necessary.

  By curing the curable resin composition with light (such as ultraviolet rays) and / or heat, a cured product [cured film (transparent film, etc.)] having excellent characteristics such as heat resistance, alkali resistance, solvent resistance, and hardness. Obtainable. The transparent film is useful as an overcoat and can also be used for a touch panel. In addition, the curable resin composition is applied on a base material (substrate, etc.), pre-baked (the solvent is removed), and light (ultraviolet light, etc.) is irradiated through a mask to cure the exposed portion, thereby unexposed portion. A desired pattern can be formed by dissolving and developing with an aqueous alkaline solution (developer). This pattern is useful, for example, as a photospacer used in a liquid crystal display device. A known or commonly used developer can be used. After development, it can be washed with water and further post-baked as necessary.

  The curable resin composition of the present invention can be used as a material for forming a liquid resist, a dry film, a photo spacer, an overcoat, a color resist, a black matrix, an insulating film and the like used for a liquid crystal display.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The weight average molecular weight and dispersity of the copolymer were measured by GPC (gel permeation chromatography; converted to polystyrene).

Example 1
A 1-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was charged with 165 g of methoxybutyl acetate and 110 g of methoxybutanol, heated to 80 ° C., then 44 g of methacrylic acid, 3 , 4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate [50:50 (molar ratio)] [compound represented by formula (11), Ra ′ = H] 281 g, dicyclopentenyl methacrylate [compound represented by formula (15), Ra ′ = CH ₃ ] A mixed solution of 25 g and azobisdimethylvaleronitrile 25 g dissolved in 350 g of methoxybutylacetate was added dropwise over 5 hours, and aged for another 3 hours. Then, it cooled to room temperature and obtained the resin solution. The polymerization reaction was performed under a nitrogen stream. The obtained resin solution is reheated to 80 ° C., and 27 g of glycidyl methacrylate, 7 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and 3 g of methoquinone are added and reacted at 80 ° C. for 10 hours. Thus, a light and / or thermosetting resin solution [solid content (NV) 36.4% by weight] was obtained. The reaction was carried out under a mixed air stream of oxygen 7 volume% and nitrogen 93 volume%. The obtained curable resin (curable copolymer) had an acid value (dry) of 48.2 KOH mg / g, a weight average molecular weight (Mw) of 12200, and a dispersity (Mw / Mn) of 2.2.

Example 2
A 1-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was charged with 160 g of methoxybutyl acetate and 110 g of methoxybutanol, heated to 80 ° C., 85 g of methacrylic acid, 3 , 4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate [50:50 (molar ratio)] [compound represented by formula (11), Ra ′ = H] 249 g, dicyclopentenyl acrylate [compound represented by formula (15), Ra ′ = H ] A mixed solution of 16 g and azobisdimethylvaleronitrile 30 g dissolved in methoxybutyl acetate 350 g was added dropwise over 5 hours, and further aged for 3 hours. The solution was cooled to a temperature to obtain a resin solution. The polymerization reaction was performed under a nitrogen stream. The obtained resin solution is reheated to 80 ° C., 47 g of glycidyl methacrylate, 7 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and 3 g of methoquinone are added and reacted at 80 ° C. for 10 hours. Thus, a light and / or thermosetting resin solution [solid content (NV) 37.6 wt%] was obtained. The reaction was carried out under a mixed air stream of oxygen 7 volume% and nitrogen 93 volume%. The obtained curable resin (curable copolymer) had an acid value (dry) of 93.3 KOH mg / g, a weight average molecular weight (Mw) of 11100, and a dispersity (Mw / Mn) of 2.4.

Example 3
A 1-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was charged with 159 g of methoxybutyl acetate and 110 g of methoxybutanol, heated to 80 ° C., then 73 g of methacrylic acid, 3 , 4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate [50:50 (molar ratio)] [compound represented by formula (11), Ra ′ = H] 256 g, dicyclopentenyl acrylate [compound represented by formula (15), Ra ′ = H ] A mixed solution of 22 g and azobisdimethylvaleronitrile 31 g dissolved in 350 g of methoxybutyl acetate was added dropwise over 5 hours, and after aging for 3 hours, The solution was cooled to a temperature to obtain a resin solution. The polymerization reaction was performed under a nitrogen stream. The obtained resin solution was reheated to 80 ° C., and 63 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE; manufactured by Nippon Kasei Co., Ltd.), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) 7 g and 3 g of methoquinone were added and reacted at 80 ° C. for 10 hours to obtain a light and / or thermosetting resin solution [solid content (NV) 38.5 wt%]. The reaction was carried out under a mixed air stream of oxygen 7 volume% and nitrogen 93 volume%. The obtained curable resin (curable copolymer) had an acid value (dry) of 71.6 KOH mg / g, a weight average molecular weight (Mw) of 10600, and a dispersity (Mw / Mn) of 2.3.

Example 4
A 1-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube was charged with 155 g of methoxybutyl acetate and 110 g of methoxybutanol, heated to 80 ° C., 91 g of acrylic acid, and styrene 73 g, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 -Mixture of yl acrylate [50:50 (molar ratio)] [compound represented by formula (11), Ra ′ = H] 174 g, dicyclopentenyl acrylate [compound represented by formula (15), Ra '= H] and a mixed solution prepared by dissolving 35 g of azobisdimethylvaleronitrile in 350 g of methoxybutylacetate was added dropwise over 5 hours. After time aging, the mixture was cooled to room temperature to obtain a resin solution. The polymerization reaction was performed under a nitrogen stream. The obtained resin solution is reheated to 80 ° C., 100 g of glycidyl methacrylate, 7 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and 3 g of methoquinone are added and reacted at 80 ° C. for 10 hours. Thus, a light and / or thermosetting resin solution [solid content (NV) 40.5% by weight] was obtained. The reaction was carried out under a mixed air stream of oxygen 7 volume% and nitrogen 93 volume%. The obtained curable resin (curable copolymer) had an acid value (dry) of 70.3 KOH mg / g, a weight average molecular weight (Mw) of 10900, and a dispersity (Mw / Mn) of 2.3.

Example 5
A 1-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was charged with 170 g of methoxybutyl acetate and 110 g of methoxybutanol, heated to 80 ° C., then 60 g of methacrylic acid, styrene 61 g, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 -Mixture of yl acrylate [50:50 (molar ratio)] [compound represented by formula (11), Ra '= H] 191 g, dicyclopentenyl acrylate [compound represented by formula (15), Ra '= H] and a mixed solution obtained by dissolving azobisdimethylvaleronitrile 20 g in methoxybutyl acetate 350 g was added dropwise over 5 hours, After aging for 3 hours, the mixture was cooled to room temperature to obtain a resin solution. The polymerization reaction was performed under a nitrogen stream. The obtained resin solution was reheated to 80 ° C., and 46 g of 3,4-epoxycyclohexylmethyl methacrylate (cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), 1,8-diazabicyclo [5.4.0] 7 g of undecene-7 (DBU) and 3 g of methoquinone were added and reacted at 80 ° C. for 10 hours to obtain a light and / or thermosetting resin solution [solid content (NV) 37.5 wt%]. The reaction was carried out under a mixed air stream of oxygen 7 volume% and nitrogen 93 volume%. The obtained curable resin (curable copolymer) had an acid value (dry) of 66.3 KOH mg / g, a weight average molecular weight (Mw) of 13200, and a dispersity (Mw / Mn) of 2.3.

Example 6
A separable flask having an internal volume of 1 liter equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube was charged with 165 g of methoxybutyl acetate and 110 g of methoxybutanol. -39 g of cyclohexylmaleimide, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Mixture of decan-8-yl acrylate [50:50 (molar ratio)] [compound represented by the above formula (11), Ra ′ = H] 196 g, dicyclopentenyl acrylate [represented by the above formula (15) Compound, Ra ′ = H] 40 g, and azobisdimethylvaleronitrile 25 g dissolved in 350 g methoxybutyl acetate for 5 hours The mixture was added dropwise over a period of 3 hours and then cooled to room temperature to obtain a resin solution. The polymerization reaction was performed under a nitrogen stream. The obtained resin solution was reheated to 80 ° C., and 40 g of 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 1,8-diazabicyclo [5.4.0] 7 g of undecene-7 (DBU) and 3 g of methoquinone were added and reacted at 80 ° C. for 10 hours to obtain a light and / or thermosetting resin solution [solid content (NV) 37.1 wt%]. The reaction was carried out under a mixed air stream of oxygen 7 volume% and nitrogen 93 volume%. The obtained curable resin (curable copolymer) had an acid value (dry) of 94.0 KOH mg / g, a weight average molecular weight (Mw) of 12500, and a dispersity (Mw / Mn) of 2.2.

Example 7
A 1-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was charged with 150 g of methoxybutyl acetate and 110 g of methoxybutanol, heated to 80 ° C., then 60 g of methacrylic acid, benzyl 67 g of methacrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane- Mixture of 8-yl acrylate [50:50 (molar ratio)] [compound represented by the above formula (11), Ra ′ = H] 167 g, dicyclopentenyl acrylate [compound represented by the above formula (15), Ra '= H] and a mixed solution of azobisdimethylvaleronitrile 40 g dissolved in methoxybutyl acetate 350 g over 5 hours. The solution was added dropwise and further aged for 3 hours, and then cooled to room temperature to obtain a resin solution. The polymerization reaction was performed under a nitrogen stream. The obtained resin solution is reheated to 80 ° C., 45 g of glycidyl methacrylate, 7 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and 3 g of methoquinone are added and reacted at 80 ° C. for 10 hours. Thus, a light and / or thermosetting resin solution [solid content (NV) 37.4% by weight] was obtained. The reaction was carried out under a mixed air stream of oxygen 7 volume% and nitrogen 93 volume%. The obtained curable resin (curable copolymer) had an acid value (dry) of 54.0 KOH mg / g, a weight average molecular weight (Mw) of 8700, and a dispersity (Mw / Mn) of 2.1.

Example 8
A 1-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was charged with 165 g of methoxybutyl acetate and 110 g of methoxybutanol, heated to 80 ° C., 95 g of acrylic acid, methyl 26 g of methacrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane- Mixture of 8-yl acrylate [50:50 (molar ratio)] [compound represented by the formula (11), Ra ′ = H] 202 g, dicyclopentenyl acrylate [compound represented by the formula (15), Ra '= H] 27 g and a mixed solution of 25 g of azobisdimethylvaleronitrile dissolved in 350 g of methoxybutyl acetate was added dropwise over 5 hours. After further aging for 3 hours, the mixture was cooled to room temperature to obtain a resin solution. The polymerization reaction was performed under a nitrogen stream. The obtained resin solution is reheated to 80 ° C., 75 g of glycidyl methacrylate, 7 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and 3 g of methoquinone are added and reacted at 80 ° C. for 10 hours. Thus, a light and / or thermosetting resin solution [solid content (NV) 39.1% by weight] was obtained. The reaction was carried out under a mixed air stream of oxygen 7 volume% and nitrogen 93 volume%. The obtained curable resin (curable copolymer) had an acid value (dry) of 104.1 KOH mg / g, a weight average molecular weight (Mw) of 12400, and a dispersity (Mw / Mn) of 2.4.

Example 9
A 1-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was charged with 165 g of methoxybutyl acetate and 110 g of methoxybutanol, heated to 80 ° C., then 75 g of methacrylic acid, styrene 46 g, 2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yloxy) ethyl acrylate and 2- (3,4-epoxytricyclo [5.2.1. 0 ² , ⁶ ] decan-8-yloxy) ethyl acrylate [50:50 (molar ratio)] [compound represented by formula (12), Ra ′ = H] 197 g, dicyclopentenyloxyethyl acrylate [ The compound represented by the above formula (16), Ra ′ = H] 33 g, and azobisdimethylvaleronitrile 30 g were mixed with methoxybutyl acetate. The mixed solution in 350g was added dropwise over 5 hours, after a further 3 hours aging and then cooled to room temperature to obtain a resin solution. The polymerization reaction was performed under a nitrogen stream. The obtained resin solution is reheated to 80 ° C., 62 g of glycidyl methacrylate, 7 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and 3 g of methoquinone are added and reacted at 80 ° C. for 10 hours. Thus, a light and / or thermosetting resin solution [solid content (NV) 38.4 wt%] was obtained. The reaction was carried out under a mixed air stream of oxygen 7 volume% and nitrogen 93 volume%. The obtained curable resin (curable copolymer) had an acid value (dry) of 59.6 KOH mg / g, a weight average molecular weight (Mw) of 10500, and a dispersity (Mw / Mn) of 2.3.

Example 10
A 1-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was charged with 155 g of methoxybutyl acetate and 110 g of methoxybutanol, heated to 80 ° C., 35 g of acrylic acid, methyl 19 g of methacrylate, 68 g of benzyl methacrylate, 2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yloxy) ethyl acrylate and 2- (3,4-epoxytricyclo [5] .2.1.0 ² , ⁶ ] decan-8-yloxy) ethyl acrylate mixture [50:50 (molar ratio)] [compound represented by formula (12), Ra ′ = H] 183 g, dicyclo [compound represented by the formula (16), Ra '= CH 3] pentenyloxy methacrylate 45 g, and Azobisujimechi The mixed solution of valeronitrile 35g in methoxybutyl acetate 350g was added dropwise over 5 hours, after a further 3 hours aging and then cooled to room temperature to obtain a resin solution. The polymerization reaction was performed under a nitrogen stream. The obtained resin solution is reheated to 80 ° C., and 27 g of glycidyl methacrylate, 7 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and 3 g of methoquinone are added and reacted at 80 ° C. for 10 hours. Thus, a light and / or thermosetting resin solution [solid content (NV) 36.4% by weight] was obtained. The reaction was carried out under a mixed air stream of oxygen 7 volume% and nitrogen 93 volume%. The obtained curable resin (curable copolymer) had an acid value (dry) of 42.9 KOH mg / g, a weight average molecular weight (Mw) of 9200, and a dispersity (Mw / Mn) of 2.0.

Comparative Example 1
A 1-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was charged with 150 g of methoxybutyl acetate and 110 g of methoxybutanol, heated to 80 ° C., then 72 g of methacrylic acid, 3 g , 4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate [50:50 (molar ratio)] [278 g of a compound represented by the formula (11), Ra ′ = H] and 40 g of azobisdimethylvaleronitrile dissolved in 350 g of methoxybutyl acetate for 5 hours The mixture was added dropwise over a period of 3 hours and then cooled to room temperature to obtain a resin solution. The polymerization reaction was performed under a nitrogen stream. The obtained resin solution is reheated to 80 ° C., 45 g of glycidyl methacrylate, 7 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and 3 g of methoquinone are added and reacted at 80 ° C. for 10 hours. Thus, a light and / or thermosetting resin solution [solid content (NV) 37.4% by weight] was obtained. The reaction was carried out under a mixed air stream of oxygen 7 volume% and nitrogen 93 volume%. The resulting curable resin (curable copolymer) had an acid value (dry) of 74.7 KOH mg / g, a weight average molecular weight (Mw) of 8800, and a dispersity (Mw / Mn) of 2.1.

Comparative Example 2
A 1-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was charged with 155 g of methoxybutyl acetate and 110 g of methoxybutanol, heated to 80 ° C., 50 g of methacrylic acid, 3 , 4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate [50:50 (molar ratio)] [300 g of the compound represented by the formula (11), Ra ′ = H] and 35 g of azobisdimethylvaleronitrile dissolved in 350 g of methoxybutyl acetate for 5 hours The mixture was added dropwise over a period of 3 hours and then cooled to room temperature to obtain a resin solution. The polymerization reaction was performed under a nitrogen stream. The obtained resin solution was reheated to 80 ° C., and 38 g of 3,4-epoxycyclohexylmethyl methacrylate (cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), 1,8-diazabicyclo [5.4.0]. 7 g of undecene-7 (DBU) and 3 g of methoquinone were added and reacted at 80 ° C. for 10 hours to obtain a light and / or thermosetting resin solution [solid content (NV) 37.0 wt%]. The reaction was carried out under a mixed air stream of oxygen 7 volume% and nitrogen 93 volume%. The obtained curable resin (curable copolymer) had an acid value (dry) of 56.3 KOH mg / g, a weight average molecular weight (Mw) of 9600, and a dispersity (Mw / Mn) of 2.2.

Comparative Example 3
A 1-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was charged with 170 g of methoxybutyl acetate and 110 g of methoxybutanol, heated to 80 ° C., 63 g of acrylic acid, styrene 65 g, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 -A mixture of yl acrylate [50:50 (molar ratio)] [compound represented by the above formula (11), Ra '= H] 221 g and azobisdimethylvaleronitrile 20 g in methoxybutyl acetate 350 g Was added dropwise over 5 hours, and further aged for 3 hours, and then cooled to room temperature to obtain a resin solution. The polymerization reaction was performed under a nitrogen stream. The obtained resin solution is reheated to 80 ° C., and 71 g of glycidyl methacrylate, 7 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and 3 g of methoquinone are added and reacted at 80 ° C. for 10 hours. Thus, a light and / or thermosetting resin solution [solid content (NV) 39.0 wt%] was obtained. The reaction was carried out under a mixed air stream of oxygen 7 volume% and nitrogen 93 volume%. The obtained curable resin (curable copolymer) had an acid value (dry) of 50.2 KOH mg / g, a weight average molecular weight (Mw) of 12700, and a dispersity (Mw / Mn) of 2.3.

Comparative Example 4
A 1-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was charged with 160 g of methoxybutyl acetate and 110 g of methoxybutanol, heated to 80 ° C., then 74 g of methacrylic acid, benzyl 38 g of methacrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane- Mixture of 8-yl acrylate mixture [50:50 (molar ratio)] [compound represented by the above formula (11), Ra ′ = H] 238 g and azobisdimethylvaleronitrile 30 g in methoxybutyl acetate 350 g The solution was added dropwise over 5 hours, and further aged for 3 hours, and then cooled to room temperature to obtain a resin solution. The polymerization reaction was performed under a nitrogen stream. The obtained resin solution was reheated to 80 ° C., and 39 g of 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 1,8-diazabicyclo [5.4.0] 7 g of undecene-7 (DBU) and 3 g of methoquinone were added and reacted at 80 ° C. for 10 hours to obtain a light and / or thermosetting resin solution [solid content (NV) 37.1 wt%]. The reaction was carried out under a mixed air stream of oxygen 7 volume% and nitrogen 93 volume%. The obtained curable resin (curable copolymer) had an acid value (dry) of 93.4 KOH mg / g, a weight average molecular weight (Mw) of 11400, and a dispersity (Mw / Mn) of 2.2.

Comparative Example 5
A 1-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was charged with 165 g of methoxybutyl acetate and 110 g of methoxybutanol, heated to 80 ° C., 80 g of acrylic acid, methyl 25 g of methacrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane- Mixture of 8-yl acrylate mixture [50:50 (molar ratio)] [compound represented by formula (11), Ra ′ = H] 245 g and azobisdimethylvaleronitrile 25 g dissolved in methoxybutyl acetate 350 g The solution was added dropwise over 5 hours, and further aged for 3 hours, and then cooled to room temperature to obtain a resin solution. The polymerization reaction was performed under a nitrogen stream. The obtained resin solution is reheated to 80 ° C., 53 g of glycidyl methacrylate, 7 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and 3 g of methoquinone are added and reacted at 80 ° C. for 10 hours. As a result, a light and / or thermosetting resin solution [solid content (NV) 37.9 wt%] was obtained. The reaction was carried out under a mixed air stream of oxygen 7 volume% and nitrogen 93 volume%. The obtained curable resin (curable copolymer) had an acid value (dry) of 103.4 KOH mg / g, a weight average molecular weight (Mw) of 12100, and a dispersity (Mw / Mn) of 2.2.

Comparative Example 6
A 1-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was charged with 155 g of methoxybutyl acetate and 110 g of methoxybutanol, heated to 80 ° C., then 52 g of methacrylic acid, N 84 g of cyclohexylmaleimide, 2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yloxy) ethyl acrylate and 2- (3,4-epoxytricyclo [5.2 .1.0 ² , ⁶ ] decan-8-yloxy) ethyl acrylate [50:50 (molar ratio)] [compound represented by formula (12), Ra ′ = H] 214 g, and azobisdimethyl A mixed solution in which 35 g of valeronitrile is dissolved in 350 g of methoxybutyl acetate is added dropwise over 5 hours, and the mixture is further aged for 3 hours. Cooled to obtain a resin solution. The polymerization reaction was performed under a nitrogen stream. The obtained resin solution is reheated to 80 ° C., 40 g of glycidyl methacrylate, 7 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and 3 g of methoquinone are added and reacted at 80 ° C. for 10 hours. Thus, a light and / or thermosetting resin solution [solid content (NV) 37.2 wt%] was obtained. The reaction was carried out under a mixed air stream of oxygen 7 volume% and nitrogen 93 volume%. The obtained curable resin (curable copolymer) had an acid value (dry) of 46.1 KOH mg / g, a weight average molecular weight (Mw) of 9400, and a dispersity (Mw / Mn) of 2.2.

(Preparation of curable resin composition and cured product)
100 g of each curable resin solution obtained in Examples and Comparative Examples was diluted with 50 g of propylene glycol monomethyl ether, and 20 g of dipentaerythritol hexaacrylate, 1-hydroxycyclohexyl-phenyl-ketone (trade name “Irgacure 184”, Ciba What added 7 g of Specialty Chemicals) was filtered through a filter having a pore size of 0.2 μm to prepare a composition solution. Moreover, about the obtained composition solution, the evaluation test was done in the following way.

(1) Hardness evaluation After the composition solution was applied on a glass substrate, it was pre-baked at 80 ° C. for 5 minutes to form a coating film having a thickness of about 3 μm. The produced coating film was cured at a high pressure mercury lamp of 120 W / cm, a height of 10 cm, and a line speed of 30 m / min, and then heated at 200 ° C. for 30 minutes to form a test coating film (test piece). The produced coating film for test was measured in accordance with JIS K-5400-1990 8.4.1 pencil scratch test, the pencil hardness was measured by scratching the coating film, and the surface hardness was measured. The results are shown in Table 1.

(2) Solvent resistance evaluation After a test piece prepared in the same manner as in the hardness evaluation test was immersed in N-methylpyrrolidone at room temperature for 30 minutes, the interface of the immersion portion and the state of the coating film of the immersion portion were visually observed. did. The evaluation criteria are as follows. The results are shown in Table 1.
◎: No change is observed ○: Only slight change is confirmed △: Dissolution of coating film and interface are observed ×: Film reduction is remarkable

(3) Heat resistance evaluation The film thickness of the test piece produced by the same method as the hardness evaluation test was measured. Then, it heated at 240 degreeC for 1 hour, and calculated the film thickness change after a reheating process by the film thickness reduction | decrease rate. The evaluation criteria are as follows. The results are shown in Table 1.
A: Thickness reduction rate of less than 5% B: Thickness reduction rate of 5% or more and less than 10% Δ: Thickness reduction rate of 10% or more and less than 15% ×: Thickness reduction rate of 15 % Or more

Claims (6)

Monomer unit (A) corresponding to carboxyl group-containing polymerizable unsaturated compound (a), the following formulas (1) and (2)

(In the formula, each R ^a represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, and each R ^b may contain a single bond or a hetero atom. An alkylene group having 1 to 18 carbon atoms)
A monomer unit (B) corresponding to the bridged alicyclic group-containing polymerizable unsaturated compound (b) having an epoxy group on at least one ring selected from the compounds represented by formula (2), and the following formula (3): And (4)

(In the formula, each R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, and each R ^d may contain a single bond or a hetero atom, respectively. An alkylene group having 1 to 18 carbon atoms)
A copolymer comprising at least a monomer unit (C) corresponding to a bridged alicyclic group-containing polymerizable unsaturated compound (c) having a double bond in at least one ring selected from the compounds represented by Light and / or thermosetting having a polymerizable unsaturated group in the side chain obtained by addition reaction of an epoxy group of the epoxy group-containing polymerizable unsaturated compound (d) with a part of the carboxyl groups of (P) Copolymer.   The light and / or heat according to claim 1, wherein the copolymer (P) further comprises other monomer units (E) in addition to the monomer units (A), the monomer units (B) and the monomer units (C). Curable copolymer. Styrene (e1) in which the monomer unit (E) may be substituted with an alkyl group or a hydroxyl group, the following formula (5)

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, R ² represents a linear or branched alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, aryl Group, aralkyl group, — (R ³ —O) _m —R ⁴ group (wherein R ³ is a divalent hydrocarbon group having 1 to 12 carbon atoms, R ⁴ is a hydrogen atom or a hydrocarbon group, and m is 1) Or a group containing a non-aromatic monocyclic or polycyclic structure]
An unsaturated carboxylic acid ester (e2) represented by the following formula (6)

(R ⁵ represents a phenyl group which may have a substituent, an aralkyl group which may have a substituent, or a cycloalkyl group which may have a substituent)
The photo- and / or thermosetting copolymer according to claim 2, which is a monomer unit corresponding to at least one polymerizable unsaturated compound selected from the group consisting of N-substituted maleimides (e3) represented by Polymer.   A curable resin composition comprising the light and / or thermosetting copolymer according to claim 1.   Furthermore, the curable resin composition of Claim 4 containing a hardening | curing agent and / or a hardening catalyst.   A cured product obtained by curing the curable resin composition according to claim 4.