Copolymer, curable resin composition, and cured product

Abstract

Provided is a copolymer which has excellent curability, production stability, and storage stability, and which is capable of imparting excellent solvent resistance to a cured product. The copolymer contains a copolymer derived from a compound represented by formula (1) (in the formula, R1a represents a hydrogen atom or an alkyl group having 1-7 carbon atoms. And R2a represents a divalent organic group. And Xa represents a heteroatom. A structural unit (A) derived from a compound (a) represented by formula (1); a structural unit (B) derived from a polymerizable unsaturated compound (b) containing an epoxy group; and a structural unit (C) derived from an addition reaction product of the compound (a) represented by formula (1) and a polymerizable unsaturated compound (c) containing an epoxy group. And a copolymer having a carboxyl group derived from the compound (a) represented by formula (1), an epoxy group derived from the polymerizable unsaturated compound (b) containing the epoxy group, and a polymerizable unsaturated group derived from the polymerizable unsaturated compound (c) containing the epoxy group. # imgabs0 #

Description

Technical Field

[0001] The present disclosure relates to a copolymer, a curable resin composition, and a cured product. In addition, this application claims priority to Japanese Patent Application No. 2022-116755 filed in Japan on July 21, 2022, the contents of which are incorporated herein by reference. Background Art

[0002] In the field of manufacturing various electronic devices that require submicron-level microfabrication, represented by VLSI, further high-density and high-integration of equipment are required. Therefore, the requirements for photolithography as a method of forming fine patterns are constantly increasing. On the other hand, in electronic components such as liquid crystal display elements, integrated circuit elements, and solid-state imaging elements, there are protective films for preventing degradation and damage, interlayer insulating films for insulating wiring arranged in layers, flattening films for flattening the surface of the element, and insulating films for ensuring electrical insulation.

[0003] A liquid crystal display element having an interlayer insulating film, such as a TFT type liquid crystal display element, can be manufactured in the following manner: a polarizing plate is disposed on a glass substrate to form a transparent conductive circuit layer such as ITO and a thin film transistor (TFT), which is then covered with an interlayer insulating film to form a back panel. On the other hand, a polarizing plate is disposed on a glass plate, and a black matrix layer and a color filter layer are patterned as needed, and a transparent conductive circuit layer and an interlayer insulating film are further sequentially formed to form an upper panel. The back panel and the upper panel are placed opposite to each other with a spacer interposed therebetween, and the liquid crystal is sealed between the two panels.

[0004] As one of the methods for forming fine patterns, a method for highly sensitizing a radiation-sensitive resin composition (resist) is known to have a chemically amplified resist using a photoacid generator as a photosensitizer. For example, a resin composition containing a copolymer containing a structural unit having an epoxy group and a photoacid generator is used, and a protonic acid is generated by the photoacid generator through exposure, so that the epoxy group is cracked and a cross-linking reaction is initiated. As a result, the copolymer becomes insoluble in the developer and a pattern is formed. In this way, compared with the existing resist whose photoreaction efficiency (reaction per photon) is less than 1, a leap in sensitivity is achieved. Most of the resists currently developed are chemically amplified, and have been used to develop highly sensitive materials corresponding to the shortening of the wavelength of the exposure light source.

[0005] For insulating films such as the interlayer insulating film provided in TFT type liquid crystal display elements and integrated circuit elements, it is necessary to implement fine patterns (fine processing). As the material for forming the insulating film, radiation-sensitive resin compositions are generally used. For such radiation-sensitive resin compositions, in order to improve productivity, it is required to have high radiation sensitivity. When the solvent resistance of the insulating film is low, the insulating film may swell, deform, and peel off from the substrate caused by organic solvents, so serious adverse conditions may occur in the manufacture of liquid crystal display elements and integrated circuit elements. Therefore, for the insulating film, excellent solvent resistance is required.

[0006] In response to such a demand, Patent Document 1 discloses a copolymer having a polymerizable unsaturated group in a side chain (a copolymer obtained by adding acrylic acid and tetrahydrophthalic anhydride to a copolymer containing glycidyl methacrylate).

[0007] In addition, Patent Document 2 discloses a method in which a highly reactive epoxy group-containing monomer is added to an epoxy group-containing monomer (3,4-epoxytricyclo[5.2.1.0 2,6 ]Decan-9-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 ] A copolymer formed by a copolymer of a mixture of a decane-8-yl acrylate) and a carboxyl group-containing monomer.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2006-11359

[0011] Patent Document 2: International Publication No. 2008 / 139679 Summary of the invention

[0012] Problems to be solved by the invention

[0013] However, the curability of the copolymer disclosed in Patent Document 1 is not considered to be sufficient. In order to improve the curability, the unsaturated groups of the copolymer need to be increased, but this results in a decrease in carboxyl groups, making it difficult to strike a balance between curability and developability.

[0014] The copolymer of Patent Document 2 has excellent storage stability and solvent resistance because it contains an epoxy-containing monomer with low reactivity with a carboxyl group. However, it has problems such as poor curability, such as requiring curing at a high temperature of 230° C. or higher and easily leaving residues during development. In addition, when the epoxy-containing monomer is changed to 3,4-epoxycyclohexylmethyl methacrylate with higher reactivity for the purpose of improving curability, there is a tendency for the reaction with the epoxy-containing monomer used in the addition reaction to reduce the production stability.

[0015] It should be noted that, in this specification, "poor storage stability" means that the weight average molecular weight of the copolymer increases over time, and "excellent storage stability" means that the weight average molecular weight of the copolymer does not increase or is not easy to increase even if it is stored for a long time. In addition, "low manufacturing stability" means that a uniform copolymer cannot be obtained when manufacturing the copolymer and gelation occurs, and "high manufacturing stability" means that a uniform copolymer can be obtained when manufacturing the copolymer and gelation is not easy to occur. It should be noted that whether the obtained copolymer is uniform can be evaluated by molecular weight distribution.

[0016] Therefore, an object of the present disclosure is to provide a copolymer having excellent curability, production stability and storage stability, which can impart excellent solvent resistance to a cured product. Another object of the present disclosure is to provide a curable resin composition containing the copolymer and a cured product thereof.

[0017] Solution to the problem

[0018] The inventors of the present disclosure have found that a copolymer including a specific structural unit has excellent curability, production stability, and storage stability, and can impart excellent solvent resistance to a cured product, thereby completing the present invention.

[0019] That is, the present disclosure provides a copolymer comprising:

[0020] The structural unit (A) derived from the compound (a) represented by the following formula (1),

[0021] The structural unit (B) derived from the polymerizable unsaturated compound (b) containing an epoxy group, and

[0022] The structural unit (C) derived from an addition reaction product of the compound (a) represented by the above formula (1) and the polymerizable unsaturated compound (c) containing an epoxy group,

[0023] [Chemical formula 1]

[0024]

[0025] (Where R 1a represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.2a represents a divalent organic group. a represents a heteroatom. )

[0026] The copolymer has:

[0027] derived from the carboxyl group of the compound (a) represented by the above formula (1),

[0028] An epoxy group derived from the above-mentioned epoxy group-containing polymerizable unsaturated compound (b), and

[0029] A polymerizable unsaturated group derived from the above-mentioned epoxy group-containing polymerizable unsaturated compound (c).

[0030] The epoxy group of the compound (b) is preferably an alicyclic epoxy group.

[0031] The epoxy group of the compound (b) is preferably a monocyclic or bicyclic alicyclic epoxy group.

[0032] In the above compound (c), it is preferred that the epoxy group and the aliphatic hydrocarbon group are bonded together.

[0033] Preferably, in the above compound (a), R 2a It represents a divalent organic group including an ester bond.

[0034] The copolymer of the present disclosure preferably further includes a structural unit (D) derived from at least one compound selected from the following (d1) to (d4).

[0035] (d1) Styrene optionally substituted with an alkyl group

[0036] (d2) N-substituted maleimide

[0037] (d3) N-vinyl compounds

[0038] (d4) unsaturated carboxylic acid derivative represented by the following formula (4)

[0039] [Chemical formula 2]

[0040]

[0041] (Where R 1d represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. 2d represents a monovalent organic group. d represents a heteroatom. )

[0042] In addition, the present disclosure provides a curable resin composition including the above copolymer.

[0043] The curable resin composition preferably further contains a photopolymerization initiator.

[0044] The curable resin composition preferably further contains a colorant.

[0045] In addition, the present disclosure provides a cured product, which is a cured product of the curable resin composition.

[0046] The cured product of the curable resin composition is preferably a color filter.

[0047] In addition, the present disclosure provides a method for producing a copolymer, the method comprising:

[0048] After copolymerization of the compound (a) represented by the following formula (1) and the epoxy-containing polymerizable unsaturated compound (b), the epoxy group of the epoxy-containing polymerizable unsaturated compound (c) is added to part of the carboxyl groups of the obtained copolymer.

[0049] [Chemical formula 3]

[0050]

[0051] (Where R 1a represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. 2a represents a divalent organic group. a represents a heteroatom. )

[0052] Effects of the Invention

[0053] The copolymer disclosed herein has excellent curability, manufacturing stability and storage stability, and can impart excellent solvent resistance to a cured product. In addition, a curable resin composition containing the copolymer has excellent curability. In addition, its cured product has excellent solvent resistance. DETAILED DESCRIPTION

[0054] <Copolymer>

[0055] The copolymers of the present disclosure comprise:

[0056] The structural unit (A) derived from the compound (a) represented by the following formula (1),

[0057] The structural unit (B) derived from the polymerizable unsaturated compound (b) containing an epoxy group, and

[0058] The structural unit (C) derived from an addition reaction product of the compound (a) represented by the above formula (1) and the polymerizable unsaturated compound (c) containing an epoxy group,

[0059] [Chemical formula 4]

[0060]

[0061] (Where R 1arepresents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. 2a represents a divalent organic group. a represents a heteroatom. )

[0062] The copolymer has:

[0063] derived from the carboxyl group of the compound (a) represented by the above formula (1),

[0064] The epoxy group derived from the above-mentioned epoxy group-containing polymerizable unsaturated compound (b), and

[0065] A polymerizable unsaturated group derived from the above-mentioned epoxy group-containing polymerizable unsaturated compound (c).

[0066] The copolymer of the present invention can be obtained by copolymerization of compounds corresponding to the above-mentioned structural units (A) to (C). In addition, the copolymer of the present invention can also be obtained by subjecting a copolymer comprising a structural unit (A) derived from a compound (a) represented by the above-mentioned formula (1) and a structural unit (B) derived from a polymerizable unsaturated compound (b) containing an epoxy group to an addition reaction with a polymerizable unsaturated compound (c) containing an epoxy group. In this case, the carboxyl group derived from the compound (a) represented by the formula (1) possessed by the above-mentioned copolymer is added to the epoxy group of the polymerizable unsaturated compound (c) containing an epoxy group to form the structural unit (C). Therefore, the structural unit (A) that has not undergone an addition reaction with the polymerizable unsaturated compound (c) containing an epoxy group has a carboxyl group derived from the compound (a) represented by the formula (1), and the structural unit (C) has a polymerizable unsaturated group derived from the polymerizable unsaturated compound (c) containing an epoxy group.

[0067] The copolymer of the present invention may further include a structural unit (D) derived from at least one compound selected from the above (d1) to (d4). That is, the copolymer of the present invention can be obtained by copolymerizing the compounds corresponding to the above structural units (A) to (C) and the compound corresponding to the structural unit (D) used as needed. In addition, it can also be obtained by subjecting a copolymer including the above structural unit (A), the above structural unit (B) and the above structural unit (D) to an addition reaction with the above compound (c).

[0068] [Structural unit (A)]

[0069] The structural unit (A) is a structural unit derived from the compound (a) represented by the above formula (1), and can be introduced into the copolymer by, for example, copolymerizing the compound (a) represented by the above formula (1) with the above-mentioned polymerizable unsaturated compound (b) containing an epoxy group. The compound (a) represented by the above formula (1) can be used alone or in combination of two or more. The copolymer disclosed in the present invention has excellent manufacturing stability and storage stability by having the above-mentioned structural unit (A).

[0070] The copolymer of the present disclosure has excellent production stability and storage stability by having the structural unit (A). The reason for this is described below using a copolymer in which the structural unit derived from (meth)acrylic acid is substituted for the structural unit (A) in the copolymer of the present disclosure as a comparative object.

[0071] (Regarding manufacturing stability)

[0072] As an embodiment, the copolymer of the present disclosure can be obtained by the following method: a copolymer comprising a structural unit (A) derived from a compound (a) represented by the above formula (1) and a structural unit (B) derived from a polymerizable unsaturated compound (b) containing an epoxy group is subjected to an addition reaction with a polymerizable unsaturated compound (c) containing an epoxy group, thereby adding the epoxy group of the above compound (c) to a part of the carboxyl groups of the above copolymer. It is believed that in the above addition reaction, since the epoxy group of the above copolymer reacts preferentially with the epoxy group of the above compound (c), an inhomogeneous copolymer is obtained, resulting in gelation (i.e., poor manufacturing stability).

[0073] In the copolymer having a structural unit derived from (meth) acrylic acid instead of the structural unit (A), the acidity of the copolymer as a whole is high, and therefore, the reactivity of the epoxy group derived from the above-mentioned compound (b) and the epoxy group of the above-mentioned compound (c) possessed by the above-mentioned copolymer is improved, and these groups react preferentially. On the other hand, the addition reaction of the carboxyl group derived from (meth) acrylic acid possessed by the above-mentioned copolymer and the epoxy group of the above-mentioned compound (c) becomes difficult to occur. As a result, sometimes the target uniform copolymer cannot be obtained, and gelation occurs. In contrast, in the copolymer disclosed in the present invention, due to the structure of the compound (a) represented by formula (1), the acidity of the copolymer as a whole is moderately reduced, and therefore, the reactivity of the epoxy group derived from the above-mentioned compound (b) possessed by the above-mentioned copolymer is reduced. As a result, the reaction of the carboxyl group derived from the compound (a) represented by formula (1) possessed by the above-mentioned copolymer and the epoxy group of the above-mentioned compound (c) is preferentially carried out, and therefore, it is easy to obtain the target uniform copolymer and gelation is not easy to occur. As such, it can be considered that the manufacturing stability of the copolymer disclosed in the present invention is excellent.

[0074] (About storage stability)

[0075] The copolymer of the present disclosure comprises a structural unit (A) derived from the compound (a) and a structural unit (B) derived from the compound (b). When the reactivity of the carboxyl group derived from the compound (a) and the epoxy group derived from the compound (b) is high, these groups react within the molecule (within the copolymer), thereby increasing the weight average molecular weight of the copolymer over time.

[0076] In the copolymer having a structural unit derived from (meth) acrylic acid instead of structural unit (A), the acidity of the copolymer as a whole is high, and therefore, the reactivity of the epoxy group derived from the above-mentioned compound (b) possessed by the above-mentioned copolymer is improved, and a reaction between the carboxyl group derived from (meth) acrylic acid and the above-mentioned epoxy group occurs. As a result, during the storage of the curable resin composition, the weight average molecular weight of the copolymer increases over time. In contrast, in the copolymer disclosed in the present invention, due to the structure of the compound (a) represented by formula (1), the acidity of the copolymer as a whole is moderately reduced, and the reactivity of the epoxy group derived from the above-mentioned compound (b) is reduced. Therefore, the reaction between the carboxyl group derived from the above-mentioned compound (a) and the epoxy group derived from the above-mentioned compound (b) becomes difficult to proceed, and there is a tendency that the weight average molecular weight of the copolymer is not easy to increase even if it is stored for a long time.

[0077] In formula (1), R 1a represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. 2a represents a divalent organic group. a Represents a heteroatom.

[0078] As R 1a Examples of the alkyl group having 1 to 7 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, and heptyl.

[0079] As R 2aThe divalent organic group in includes, for example, alkylene groups such as methylene, ethylene, propylene, trimethylene (preferably alkylene groups having 1 to 20 carbon atoms, more preferably alkylene groups having 1 to 12 carbon atoms, further preferably alkylene groups having 1 to 6 carbon atoms, and particularly preferably alkylene groups having 1 to 3 carbon atoms), alkenylene groups (preferably alkenylene groups having 2 to 20 carbon atoms, more preferably alkenylene groups having 2 to 12 carbon atoms, and further preferably alkenylene groups having 2 to 6 carbon atoms), cycloalkylene groups, arylene groups, and groups in which a plurality of these groups are connected directly or via a connecting group. The connecting group includes, for example, an ether bond, a carbonyl group, an ester bond, a thioether bond, and an amide group, and from the viewpoint of manufacturing stability and storage stability, an ester bond is preferred. By making the divalent organic group include an ester bond, the acidity of the copolymer including the structural unit (A) is moderately reduced, and thus there is a tendency for manufacturing stability and storage stability to be improved.

[0080] The divalent organic group is not particularly limited, but is preferably a group in which two alkylene groups (preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms) are bonded via a linking group, more preferably a group in which the two alkylene groups are bonded via an ester bond, and further preferably -C 2 H 4 -O-(C=O)-C 2 H 4 -Base (from the left side of C 2 H 4 The bond arm extending to the left of the base and the X a Bonding, from the right side of C 2 H 4 The bond arm extending to the right of the (C=O)-OH group is bonded to the carbon atom of the (C=O)-OH group).

[0081] The number of carbon atoms (total number) in the divalent organic group is not particularly limited, and is, for example, preferably 1 to 15, more preferably 2 to 10, and still more preferably 3 to 6. By setting the number of carbon atoms (total number) in the divalent organic group to be within the above range, the acidity of the carboxyl group derived from the compound (a) represented by the formula (1) is moderately reduced, and thus the curability, production stability, and storage stability of the copolymer tend to be improved.

[0082] X a The hetero atom in is not particularly limited, and examples thereof include a nitrogen atom, an oxygen atom, and a sulfur atom, and an oxygen atom is preferred.

[0083] The proportion of the structural unit (A) in the copolymer is not particularly limited, and for example, it is preferably 10 to 50 mol% relative to all the structural units constituting the copolymer, and its lower limit is more preferably 20 mol%, and its upper limit is more preferably 40 mol%. By making the proportion of the structural unit (A) above the above lower limit, there is a tendency for excellent developability. By making the proportion of the structural unit (A) below the above upper limit, excessive development can be suppressed, and thus there is a tendency for excellent solvent resistance. It should be noted that in the present disclosure, the proportion of the structural unit in the copolymer is a ratio based on the molar amount of the compound (monomer) used in the copolymer. For example, the proportion of the structural unit (A) in the copolymer refers to the ratio of the amount of the compound (a) represented by formula (1) relative to the total amount (100 mol%) of the compound used in the copolymer. Among them, among the structural units derived from the compound (a) represented by formula (1), the structural unit to which the epoxy group of the polymerizable unsaturated compound (c) containing an epoxy group is added becomes the structural unit (C), which is not included in the structural unit (A). Therefore, the proportion of the structural unit (A) in the copolymer is calculated by subtracting the amount of the epoxy group-containing polymerizable unsaturated compound (c) from the amount of the compound (a) represented by the formula (1) used.

[0084] [Structural unit (B)]

[0085] The structural unit (B) is a structural unit derived from a polymerizable unsaturated compound (b) containing an epoxy group, and can be introduced into a copolymer by, for example, copolymerizing a polymerizable unsaturated compound (b) containing an epoxy group with a compound (a) represented by the above formula (1). The polymerizable unsaturated compound (b) containing an epoxy group can be used alone or in combination of two or more.

[0086] The above-mentioned compound (b) is not particularly limited as long as it is a compound containing an epoxy group and a polymerizable unsaturated group, and the epoxy group is preferably an alicyclic epoxy group. That is, the above-mentioned compound (b) is preferably a compound containing an alicyclic epoxy group and a polymerizable unsaturated group (a polymerizable unsaturated compound containing an alicyclic epoxy group). It should be noted that the alicyclic ring in the alicyclic epoxy group may have a substituent other than an epoxy group. In addition, in this specification, "alicyclic epoxy group" refers to an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. By making the above-mentioned compound (b) a polymerizable unsaturated compound containing an alicyclic epoxy group, there is a tendency for the manufacturing stability and curability of the copolymer disclosed in the present invention to be improved. It can be considered that this is because the reactivity of the alicyclic epoxy group in the above-mentioned compound is moderately low, and therefore, it is not easy to react with the epoxy group derived from the polymerizable unsaturated compound (c) containing an epoxy group.

[0087] Examples of the alicyclic epoxy group include an epoxycyclohexyl group, a 2,3-epoxybicyclo[2.2.1]heptyl group, a 2,3-epoxy-7-oxabicyclo[2.2.1]heptyl group, a 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl (3,4-epoxydicyclopentyl), and groups having substituents on one or more carbon atoms constituting these groups.

[0088] From the viewpoint of the curability, manufacturing stability and storage stability of the copolymer, the epoxy group in the above-mentioned compound (b) is preferably a monocyclic or bicyclic (wherein the ring formed by the epoxy group is not counted) alicyclic epoxy group. In addition, the above-mentioned alicyclic epoxy group preferably has an epoxycyclohexyl skeleton. In the case where the above-mentioned alicyclic epoxy group has an epoxycyclohexyl skeleton, the above-mentioned compound (b) is preferably bonded to the polymerizable unsaturated group via the carbon atom at the 3rd or 4th position of the above-mentioned skeleton.

[0089] Examples of the alicyclic epoxy group-containing polymerizable unsaturated compound include compounds represented by the following formula (2).

[0090] [Chemical formula 5]

[0091]

[0092] In formula (2), R 1b represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. 2b are the same or different and represent an alkyl group having 1 to 7 carbon atoms. b represents a single bond or a divalent organic group. 2b The substituents on the cyclohexane ring shown in formula (2) are not included in Y b Substituents possessed by Y b Indicates non-bonding (meaning there is no b ), a methylene group or an ethylene group optionally having an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom optionally bonded to an oxygen atom. n represents an integer greater than 0 (preferably an integer of 0 to 7).

[0093] As R 1b The alkyl group having 1 to 7 carbon atoms in the group includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, heptyl, etc. From the viewpoint of copolymerizability and reactivity, R 1b Preferred is a hydrogen atom, a methyl group or an ethyl group.

[0094] As R 2bThe alkyl group having 1 to 7 carbon atoms in the group includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, heptyl, etc. When n is 2 or more, n R 2b From the viewpoint of copolymerizability and reactivity, R 2b Preferred is methyl or ethyl.

[0095] As X b The divalent organic group in the group includes, for example, alkylene groups such as methylene, ethylene, propylene, and trimethylene (preferably alkylene groups having 1 to 20 carbon atoms, more preferably alkylene groups having 1 to 12 carbon atoms, further preferably alkylene groups having 1 to 6 carbon atoms, and particularly preferably alkylene groups having 1 to 3 carbon atoms), alkenylene groups (preferably alkenylene groups having 2 to 20 carbon atoms, more preferably alkenylene groups having 2 to 12 carbon atoms, and further preferably alkenylene groups having 2 to 6 carbon atoms), cycloalkylene groups, arylene groups, and groups in which a plurality of these groups are connected directly or via a connecting group. Examples of the connecting group include, for example, ether bonds, carbonyl groups, ester bonds, thioether bonds, and amide groups.

[0096] X b It is preferably bonded to the carbon atom at the 3-position or 4-position of the epoxycyclohexyl skeleton shown in formula (2).

[0097] As Y, an alkyl group which may have 1 to 3 carbon atoms b The methylene group or ethylene group as the substituent is not particularly limited, but is preferably a methylene group or an ethylene group, and more preferably a methylene group.

[0098] As an option with Y b The sulfur atom bonded to the oxygen atom of the group includes, for example, a sulfur atom, a sulfonyl group, and the like.

[0099] Examples of the compound represented by the above formula (2) include compounds represented by the following formula (2').

[0100] [Chemical formula 6]

[0101]

[0102] R in formula (2') 1b , R 2b , X b , Y b and n are the same as those described in formula (2).

[0103] Specific examples of the compound represented by formula (2) include the following compounds.

[0104] [Chemical formula 7]

[0105]

[0106] [Chemical formula 8]

[0107]

[0108] The proportion of the structural unit (B) in the copolymer is not particularly limited, but is preferably 5 to 40 mol% relative to all the structural units constituting the copolymer, and its lower limit is more preferably 10 mol%, and further preferably 15 mol%. In addition, its upper limit is more preferably 35 mol%, and further preferably 30 mol%. By making the proportion of the structural unit (B) within the above range, the epoxy group contained in the copolymer is an amount suitable for curing, so even if curing is performed at a relatively low temperature, the cross-linked structure of the cured product becomes denser, and thus has a tendency to be excellent in solvent resistance.

[0109] [Structural unit (C)]

[0110] The structural unit (C) is a structural unit derived from an addition reaction product of the compound (a) represented by the above formula (1) and the polymerizable unsaturated compound (c) containing an epoxy group. Specifically, it is a structural unit of a compound obtained by adding an epoxy group of the polymerizable unsaturated compound (c) containing an epoxy group to the carboxyl group of the compound (a) represented by the above formula (1).

[0111] The above-mentioned polymerizable unsaturated compound (c) containing an epoxy group is not particularly limited as long as it is a compound containing an epoxy group and a polymerizable unsaturated group, and may be the same as the above-mentioned compound (b), but from the viewpoint of manufacturing stability, it is preferably different from the above-mentioned polymerizable unsaturated compound (b) containing an epoxy group. In the polymerizable unsaturated compound (c) containing an epoxy group, the epoxy group is more preferably a group bonded to an aliphatic hydrocarbon group (aliphatic epoxy group), and is particularly preferably a glycidyl group. The polymerizable unsaturated compound (c) containing an epoxy group can be used alone or in combination of two or more.

[0112] Examples of the compound (c) include allyl glycidyl ether, glycidyl (meth)acrylate, 2-methyl glycidyl (meth)acrylate, 2-ethyl glycidyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxypropyl (meth)acrylate, glycidyloxyphenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate glycidyl ether, and 4-hydroxybutyl (meth)acrylate glycidyl ether. Among them, glycidyl (meth)acrylate is preferred from the viewpoint of improving production stability and curability.

[0113] In the copolymer disclosed in the present invention, when the compound (b) is a polymerizable unsaturated compound containing an alicyclic epoxy group, and the compound (c) is a polymerizable unsaturated compound containing an aliphatic epoxy group (particularly a polymerizable unsaturated compound containing a glycidyl group), not only is the production stability and storage stability excellent, but also curing occurs even at a relatively low temperature, and the cured product has excellent solvent resistance. The reasons for such a remarkable effect are considered to be as follows: [1] The epoxy group of the polymerizable unsaturated compound containing an aliphatic epoxy group has a high reactivity relative to the polymerizable unsaturated compound containing an alicyclic epoxy group. Therefore, the carboxyl group derived from the compound (a) represented by the formula (1) reacts preferentially with the epoxy group of the polymerizable unsaturated compound containing an aliphatic epoxy group, thereby achieving excellent production stability; [2] The epoxy group derived from the polymerizable unsaturated compound containing an alicyclic epoxy group has a moderately low reactivity. Therefore, it is less likely to react with the carboxyl group derived from the compound (a) represented by the formula (1), thereby achieving excellent storage stability; [3] The carboxyl group derived from the compound (a) represented by the formula (1), the epoxy group derived from the polymerizable unsaturated compound containing an alicyclic epoxy group, and the polymerizable unsaturated group derived from the polymerizable unsaturated compound containing an aliphatic epoxy group in the copolymer are present in a well-balanced manner, thereby contributing to an improvement in curability.

[0114] The proportion (content) of the structural unit (C) in the copolymer is not particularly limited, for example, preferably 10 to 60 mol% relative to all the structural units constituting the copolymer, and the lower limit is more preferably 15 mol%. In addition, the upper limit is more preferably 50 mol%, and further preferably 35 mol%. By making the proportion of the structural unit (C) above the above lower limit, due to the presence of the polymerizable unsaturated group derived from the polymerizable unsaturated compound (c) containing an epoxy group, there is a tendency to solidify even at a relatively low temperature. By making the proportion of the structural unit (C) below the above upper limit, the hydroxyl group contained in the copolymer is an appropriate amount, and therefore, in particular, there is a tendency to have excellent solvent resistance to solvents with high polarity. In addition, since the copolymer becomes hydrophilic, it has a tendency to have excellent developability (fast development speed, less residue). It should be noted that in the present disclosure, the proportion of the structural unit (C) in the copolymer can be calculated as follows: assuming that all the polymerizable unsaturated compounds (c) containing epoxy groups used react with the carboxyl groups of the compound (a) represented by formula (1), the calculation is based on the molar amount of the polymerizable unsaturated compounds (c) containing epoxy groups.

[0115] [Structural unit (D)]

[0116] The structural unit (D) is a structural unit derived from at least one compound selected from the group consisting of styrene (d1) optionally substituted with an alkyl group, N-substituted maleimide (d2), N-vinyl compound (d3) and unsaturated carboxylic acid derivative (d4) represented by the above formula (2). The structural unit (D) has the function of imparting hardness to the cured product (cured film), the function of allowing the copolymerization reaction to proceed smoothly, the function of improving solubility in a solvent, the function of improving adhesion to a substrate, and the like.

[0117] The structural unit (D) can be introduced into the copolymer by copolymerizing at least one compound selected from the above (d1) to (d4) with the compound (a) represented by the above formula (1) and the above epoxy-containing polymerizable unsaturated compound (b).

[0118] (Styrene (d1))

[0119] The alkyl group in the styrene (d1) which may be substituted with an alkyl group is not particularly limited, and examples thereof include alkyl groups having 1 to 7 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and hexyl. Among them, alkyl groups having 1 to 4 carbon atoms, such as methyl or ethyl, are preferred, and methyl is more preferred. The above alkyl groups may be bonded to any position in the vinyl group and the benzene ring of styrene.

[0120] Representative examples of the styrene (d1) optionally substituted with an alkyl group include styrene, α-methylstyrene, vinyltoluene (o-vinyltoluene, m-vinyltoluene, p-vinyltoluene), etc. Among them, styrene is preferred. The styrene (d1) optionally substituted with an alkyl group may be used alone or in combination of two or more.

[0121] (N-substituted maleimide (d2))

[0122] Examples of the N-substituted maleimide (d2) include compounds represented by the following formula (3).

[0123] [Chemical formula 9]

[0124]

[0125] In formula (3), R 1 It represents a monovalent organic group.

[0126] Examples of the monovalent organic group include hydrocarbon groups and heterocyclic groups. Examples of the hydrocarbon group include alkyl groups (e.g., alkyl groups having 1 to 6 carbon atoms) such as methyl, ethyl, propyl, isopropyl, butyl, and hexyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, and norbornyl; aryl groups such as phenyl; aralkyl groups such as benzyl; and groups formed by bonding two or more of these groups. Examples of the heterocyclic group include 5- to 10-membered heterocycloalkyl and heteroaryl groups containing at least one hetero atom selected from nitrogen, oxygen, and sulfur atoms.

[0127] There are no particular limitations on the N-substituted maleimide (d2), and examples thereof include: N-alkyl maleimides such as N-methyl maleimide, N-ethyl maleimide, and N-propyl maleimide; N-cycloalkyl maleimides such as N-cyclopentyl maleimide, N-cyclohexyl maleimide, N-cyclooctyl maleimide, N-adamantyl maleimide, and N-norbornyl maleimide; N-aryl maleimides such as N-phenyl maleimide; N-aralkyl maleimides such as N-benzyl maleimide, etc. Among them, N-cyclohexyl maleimide is preferred. The N-substituted maleimide (d2) can be used alone or in combination of two or more.

[0128] (N-vinyl compound (d3))

[0129] The N-vinyl compound (d3) is not particularly limited, and examples thereof include N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methylacetamide, N-vinyl pyrrolidone, N-vinyl carbazole, N-vinyl piperidone, N-vinyl caprolactam, etc. The N-vinyl compound (d3) may be used alone or in combination of two or more thereof.

[0130] (Unsaturated carboxylic acid derivative (d4))

[0131] The unsaturated carboxylic acid derivative (d4) is represented by the following formula (4).

[0132] [Chemical formula 10]

[0133]

[0134] In formula (4), R 1d represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. 2d represents a monovalent organic group. d Represents a heteroatom.

[0135] As R 1dThe alkyl group having 1 to 7 carbon atoms in the group may be, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, or the like. 1d , particularly preferably a hydrogen atom or a methyl group.

[0136] As R 2d The monovalent organic group in R includes, for example, carboxyl, alkyl, heteroalkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, and groups formed by bonding two or more of these groups. 2d The carbon atom in the monovalent organic group is bonded to X d .

[0137] Examples of the alkyl group include alkyl groups having 1 to 23 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, hexyl, octyl, decyl, dodecyl, isodecyl, lauryl and stearyl.

[0138] Examples of the heteroalkyl group include: -(R 2d1 -O)pR 2d2 Base (where R 2d1 represents an alkylene group having 1 to 12 carbon atoms. 2d2 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. p represents an integer greater than 1), -R 2d3 -NR 2d4 R 2d5 Base (where R 2d3 represents an alkylene group having 1 to 12 carbon atoms. 2d4 and R 2d5 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).

[0139] Examples of the alkenyl group include alkenyl groups having 2 to 23 carbon atoms, such as allyl group, 3-butenyl group, and 5-hexenyl group.

[0140] Examples of the cycloalkyl group include cycloalkyl groups having 3 to 12 carbon atoms, such as cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, and norbornyl.

[0141] Examples of the heterocycloalkyl group include groups containing a cyclic ether structure such as an oxetane ring, an oxolan ring, an oxhenane ring, and an oxepane ring (for example, groups containing a cyclic ether having a three-membered ring or more).

[0142] Examples of the aryl group include aryl groups having 6 to 12 carbon atoms, such as phenyl and naphthyl.

[0143] Examples of the hetero atom in X include a nitrogen atom, an oxygen atom, and a sulfur atom.

[0144] The unsaturated carboxylic acid derivative (d4) represented by the formula (4) is not particularly limited, and examples thereof include (meth)acrylates having an alkyl group such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; (meth)acrylates having an alkylamino group such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and N,N-diisopropylaminoethyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylate. (meth)acrylates containing a hydroxyl group such as 2-hydroxybutyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate, (meth)acrylates containing a heteroalkyl group such as methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, isooctyloxydiethylene glycol (meth)acrylate, phenoxytriethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate; (meth)acrylates containing an alkenyl group such as allyl (meth)acrylate; cyclohexyl (meth)acrylate, 1-adamantyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5,2,1,0 2,6] decan-8-ol (meth)acrylate having a monocyclic or polycyclic cycloalkyl group; (meth)acrylate oxetane, (meth)acrylate 3-methyl-3-oxetane, (meth)acrylate 3-ethyl-3-oxetane, (meth)acrylate (3-methyl-3-oxetane)methyl, (meth)acrylate (3-ethyl-3-oxetane)methyl, (meth)acrylate 2-(3-methyl-3-oxetane)ethyl, (meth)acrylate 2-(3-ethyl-3-oxetane)ethyl, (meth)acrylate 2-[(3-methyl-3-oxetane)methyl] (meth)acrylates having a heterocycloalkyl group (for example, a group containing a cyclic ether having a three-membered ring or more) such as (meth)acrylates having an oxetane group such as (meth)ethyl (meth)acrylate, 2-[(3-ethyl-3-oxetanyl)methyloxy]ethyl (meth)acrylate, 3-[(3-methyl-3-oxetanyl)methyloxy]propyl (meth)acrylate, and 3-[(3-ethyl-3-oxetanyl)methyloxy]propyl (meth)acrylate, and (meth)acrylates having an oxetane group such as tetrahydrofurfuryl (meth)acrylate; (meth)acrylates having an aryl group such as phenyl (meth)acrylate and benzyl (meth)acrylate. The unsaturated carboxylic acid derivative (d4) represented by formula (2) can be used alone or in combination of two or more. Among them, preferred are (meth)acrylates having an alkyl group and (meth)acrylates having an aryl group, and more preferred are methyl (meth)acrylate, butyl (meth)acrylate, and benzyl (meth)acrylate.

[0145] The proportion (content) of the structural unit (D) in the copolymer is not particularly limited, and is preferably 0 to 50 mol% relative to all the structural units constituting the copolymer, and its lower limit is more preferably 1 mol%, and its upper limit is more preferably 35 mol%. By making the proportion of the structural unit (D) 1 mol% or more (particularly 5 mol% or more), there is a tendency to effectively exert the function of imparting hardness to the cured product (cured film), the function of making the copolymerization reaction proceed smoothly, the function of improving solubility in the solvent, the function of improving the adhesion to the substrate, etc. When the proportion of the structural unit (D) is below the above-mentioned upper limit, the proportion of the structural units (A) to (C) increases relatively, and therefore there is a tendency to effectively exert the functions of these structural units.

[0146] When the copolymer of the present disclosure contains the structural unit (A), the structural unit (B) and the structural unit (C) but does not contain the structural unit (D), the total amount of the structural units (A) to (C) is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more, relative to all the structural units constituting the copolymer, and may be substantially 100 mol%. In addition, when the copolymer of the present disclosure contains the structural unit (A), the structural unit (B), the structural unit (C) and the structural unit (D), the total amount of the structural units (A) to (D) is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more, relative to all the structural units constituting the copolymer, and may be substantially 100 mol%.

[0147] The weight average molecular weight (Mw) of the copolymer disclosed in the present invention is not particularly limited, and is preferably 5,000 to 70,000, and more preferably 7,000 to 20,000. The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight: Mw / Mn) of the copolymer disclosed in the present invention is not particularly limited, and is preferably 3.5 or less (e.g., 1.1 to 3.5), and more preferably 2.5 or less (1.1 to 2.5). The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured, for example, by GPC using polystyrene as a standard substance, and are preferably measured by the method used in the examples.

[0148] The acid value of the copolymer disclosed in the present invention is, for example, about 30 to 120 mgKOH / g, preferably about 40 to 100 mgKOH / g. When the acid value is within the above range, there is a tendency for excellent developability. It should be noted that the method for measuring the acid value of the copolymer is not particularly limited, and it can be measured, for example, by the method described in the examples.

[0149] The copolymer disclosed in the present invention has excellent manufacturing stability and storage stability, and excellent curing properties. That is, curing will occur even at a relatively low temperature, and the cured product has excellent solvent resistance. In addition, the curable resin composition comprising the above-mentioned copolymer has excellent storage stability, curing will occur at a relatively low temperature, and the cured product has excellent solvent resistance. Further, its cured product is useful as a material for forming a protective film or an insulating film because it has excellent solvent resistance and high insulation. In addition, the cured product of the copolymer disclosed in the present invention is useful as an adhesive resin or a pigment dispersion resin because it has excellent storage stability.

[0150] <Method for producing copolymer>

[0151] The copolymer disclosed in the present invention can be obtained by copolymerizing the compounds corresponding to the above-mentioned structural units (A) to (C) and the compound corresponding to the above-mentioned structural unit (D) used as needed. In addition, the copolymer disclosed in the present invention can be produced by copolymerizing the compound (a) represented by the above-mentioned formula (1), the polymerizable unsaturated compound (b) containing an epoxy group, and at least one compound selected from the above-mentioned (d1) to (d4) used as needed, and then adding the epoxy group of the polymerizable unsaturated compound (c) containing an epoxy group to a part of the carboxyl groups of the obtained copolymer. Hereinafter, compounds that can be introduced into the copolymer, such as the compound (a) represented by formula (1), are sometimes collectively referred to as "monomers".

[0152] The copolymerization reaction of the monomers can also be carried out in the presence of a polymerization initiator. As the above-mentioned polymerization initiator, a conventional or well-known free 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), 2,2'-azobis(2-methylpropionic acid) dimethyl ester, 2,2'-azobis(2-methylpropionic acid) diethyl ester, 2,2'-azobis(2-methylpropionic acid) dibutyl ester and other azo compounds, benzoyl peroxide, lauroyl peroxide, tert-butyl peroxypivalate, 1,1-bis(tert-butylperoxy)cyclohexane and other organic peroxides, hydrogen peroxide and the like. When a peroxide is used as a free radical polymerization initiator, a reducing agent can be combined to form a redox initiator. Among them, an azo compound is preferred, and 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(2-methylpropionic acid)dimethyl ester are more preferred.

[0153] The amount of the polymerization initiator used is not particularly limited as long as it does not hinder smooth progress of the copolymerization reaction, and is, for example, preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, based on the total amount of the monomers (100 parts by weight).

[0154] The copolymerization reaction can be carried out by conventional methods used in the manufacture of acrylic polymers and styrene polymers, such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, and emulsion polymerization. The monomer and polymerization initiator can be supplied to the reaction system at once, or part or all of them can be added dropwise to the reaction system. For example, a method of polymerizing by dropping a solution obtained by dissolving a polymerization initiator in a polymerization solvent into a monomer or a mixed solution of a monomer and a polymerization solvent maintained at a certain temperature; a method of polymerizing by dropping a solution obtained by dissolving a monomer and a polymerization initiator in a polymerization solvent in advance into a polymerization solvent maintained at a certain temperature (drop polymerization method), etc.

[0155] The polymerization solvent can be appropriately selected according to the monomer composition, and examples thereof include: ethers (ethyl ether; ethylene glycol mono- or dialkyl ethers, diethylene glycol mono- or dialkyl ethers, propylene glycol mono- or dialkyl ethers, propylene glycol mono- or diaryl ethers, dipropylene glycol mono- or dialkyl ethers, tripropylene glycol mono- or dialkyl ethers, 1,3-propylene glycol mono- or dialkyl ethers, 1,3-butanediol mono- or dialkyl ethers, 1,4-butanediol mono- or dialkyl ethers, glycerol mono-, di- or trialkyl ethers, etc.; chain ethers of glycol ethers such as tetrahydrofuran, dimethicone ... alkyl and other cyclic ethers, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, C 5-6 Cycloalkanediol mono- or diacetate, C 5-6 Carboxylic acid esters such as cycloalkane dimethanol mono- or diacetate; ethylene glycol mono-alkyl ether acetate, ethylene glycol mono- or diacetate, diethylene glycol mono-alkyl ether acetate, diethylene glycol mono- or diacetate, propylene glycol mono-alkyl ether acetate, propylene glycol mono- or diacetate, dipropylene glycol mono-alkyl ether acetate, dipropylene glycol mono- or diacetate, 1,3-propylene glycol mono-alkyl ether acetate, 1,3-propylene glycol mono- or diacetate, 1,3-butylene glycol mono-alkyl ether acetate, 1,3-butylene glycol mono- or diacetate, 1,4-butylene glycol mono-alkyl ether acetate, 1,4-butylene glycol mono- or diacetate, glycerol mono-, di- or triacetate, glycerol mono- or di-C 1-4 alkyl ether di- or monoacetates, tripropylene glycol monoalkyl ether acetate, tripropylene glycol mono- or diacetate, etc. glycol acetates or glycol ether acetates, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexene-1-one, etc.), amides (N,N-dimethylacetamide, N,N-dimethylformamide, etc.), sulfoxides (dimethyl sulfoxide, etc.), alcohols (methanol, ethanol, propanol, C 5-6 Cycloalkanediol, C 5-6 cycloalkane dimethanol, etc.), hydrocarbons (aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, etc.), mixed solvents thereof, etc.

[0156] The reaction temperature in the polymerization reaction can be appropriately selected depending on the type and composition of the monomers and is not particularly limited, but is preferably 30 to 150°C, for example.

[0157] Hereinafter, a method for producing the copolymer of the present invention is described in which the compound (a) represented by the above formula (1), the polymerizable unsaturated compound (b) containing an epoxy group, and at least one compound selected from the above (d1) to (d4) used as required are copolymerized, and then the epoxy groups of the polymerizable unsaturated compound (c) containing an epoxy group are added to a part of the carboxyl groups of the obtained copolymer.

[0158] The addition reaction of the above-mentioned compound (C) can be carried out in the presence of a catalyst. Examples of the above-mentioned catalyst include tertiary amines such as dimethylbenzylamine, triethylamine, tetramethylethylenediamine, tri-n-octylamine, and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU); quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, and tetrabutylammonium bromide; alkyl ureas such as tetramethylurea; alkyl guanidines such as tetramethylguanidine; metal compounds (metal salts, etc.) such as cobalt naphthenate; organic metal complexes; phosphine compounds (especially tertiary phosphines) such as triphenylphosphine, etc. These catalysts can be used alone or in combination of two or more.

[0159] The amount of the catalyst used is not particularly limited, but is preferably 0.01 to 30% by weight, for example, with respect to the polymerizable unsaturated compound (c) containing an epoxy group, and its lower limit is more preferably 0.1% by weight, and further preferably 1% by weight. In addition, its upper limit is more preferably 25% by weight, and further preferably 20% by weight.

[0160] The addition reaction is usually carried out in the presence of a solvent. The solvent is not particularly limited as long as it can dissolve the raw materials, and for example, the solvents exemplified as the above-mentioned polymerization solvents can be used.

[0161] The reaction temperature during the addition reaction is not particularly limited, and is, for example, preferably 10 to 150° C., more preferably 60 to 100° C. During the addition reaction, a polymerization inhibitor may be added to the reaction system in order to suppress gelation caused by polymerization of the polymerizable unsaturated group. Examples of the polymerization inhibitor include p-hydroxyanisole (methoquinone), hydroquinone, hydroquinone monomethyl ether, and phenothiazine.

[0162] In the method for producing the copolymer disclosed in the present invention, the obtained reaction product can be purified by precipitation or reprecipitation as needed. The solvent used for precipitation or reprecipitation can be any solvent in an organic solvent and water, and can also be a mixed solvent thereof. Examples of organic solvents include hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene), halogenated hydrocarbons (halogenated aliphatic hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, etc.), nitro compounds (nitromethane, nitroethane, etc.), nitriles (acetonitrile, benzonitrile, etc.), ethers (chain ethers such as diethyl ether, diisopropyl ether, and dimethoxyethane; tetrahydrofuran, dimethoxyethane, etc.); The invention also includes cyclic ethers such as alkanes, ketones (acetone, methyl ethyl ketone, diisobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, etc.), carbonates (dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), alcohols (methanol, ethanol, propanol, isopropanol, butanol, etc.), carboxylic acids (acetic acid, etc.), and mixed solvents containing these solvents.

[0163] <Curable resin composition>

[0164] The curable resin composition of the present disclosure is characterized by containing the copolymer of the present disclosure. In addition, it may contain a curable compound other than the copolymer of the present disclosure, a photopolymerization initiator, and a solvent.

[0165] The curable compound other than the copolymer of the present disclosure is not particularly limited, and examples thereof include polyfunctional vinyl compounds, polyfunctional thiol compounds, and polyfunctional epoxy compounds.

[0166] The polyfunctional vinyl compound is not particularly limited as long as it is a compound having two or more vinyl groups, and examples thereof include: di(meth)acrylates of alkylene glycols such as ethylene glycol and propylene glycol; di(meth)acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; di(meth)acrylates of dual-terminal hydroxylated polymers such as dual-terminal hydroxyl polybutadiene, dual-terminal hydroxyl polyisoprene, and dual-terminal hydroxyl polycaprolactone; glycerol, 1,2,4-butanetriol, trimethylolalkane, tetramethylol Poly (meth) acrylates of trivalent or higher polyols such as alkanes, pentaerythritol, and dipentaerythritol (e.g., dipentaerythritol hexaacrylate); poly (meth) acrylates of polyalkylene glycol adducts of trivalent or higher polyols; poly (meth) acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediol; oligo (meth) acrylates such as polyester (meth) acrylates, epoxy (meth) acrylates, urethane (meth) acrylates, and silicone resin (meth) acrylates. The multifunctional vinyl compound may be used alone or in combination of two or more.

[0167] The polyfunctional thiol compound is not particularly limited as long as it is a compound having two or more thiol groups, and examples thereof include hexanedithiol, decanedithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol dithioglycolate, ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrathioglycolate, pentaerythritol tetrathiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylthiopropionate, The polyfunctional thiol compounds include 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, tetraethylene glycol bis-3-mercaptopropionate, trimethylolpropane tris-3-mercaptopropionate, tris(3-mercaptopropionyloxyethyl)isocyanurate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and pentaerythritol tetrakis(3-mercaptobutyrate). The polyfunctional thiol compounds may be used alone or in combination of two or more.

[0168] The polyfunctional epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups, and examples thereof include: glycidyl ethers (e.g., ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, etc.) generated by the reaction of a glycidyl ether-type epoxy compound [a polyhydroxy compound (bisphenols, polyphenols, alicyclic polyols, aliphatic polyols, etc.) with epichlorohydrin, (poly)C 2-4 Alkylene glycol diglycidyl ether; diglycidyl ether of polyphenols such as resorcinol and hydroquinone; diglycidyl ether of alicyclic polyols such as cyclohexanediol, cyclohexanedimethanol, and hydrogenated bisphenols; bisphenols (bis(hydroxyphenyl)alkanes such as 4,4'-dihydroxybiphenyl and bisphenol A) or their C 2-3diglycidyl ether of alkylene oxide adduct, etc.), novolac type epoxy resin (phenol novolac type or cresol novolac type epoxy resin, etc.)], glycidyl ester type epoxy compound, alicyclic epoxy compound (or cyclic aliphatic epoxy resin), heterocyclic epoxy resin (triglycidyl isocyanurate (TGIC), hydantoin type epoxy resin, etc.), glycidylamine type epoxy compound [reaction product of amine and epichlorohydrin, for example, N-glycidyl aromatic amine {tetraglycidyl diaminodiphenylmethane (TGDDM), triglycidyl aminophenol (TGPAP, TGMAP, etc.), diglycidyl aniline (DGA), diglycidyl toluidine (DGT), tetraglycidyl benzyl dimethyl diamine (TGMXA, etc.)}, N-glycidyl alicyclic amine (tetraglycidyl bisaminocyclohexane, etc.)], etc. The polyfunctional epoxy compound can be used alone or in combination of two or more.

[0169] In the present disclosure, the photopolymerization initiator is not particularly limited, and examples thereof include a photoradical polymerization initiator and a photocationic polymerization initiator.

[0170] The photoradical polymerization initiator is a compound that generates radicals by irradiation with light and initiates a curing reaction (radical polymerization) of the photopolymerizable compound contained in the curable resin composition. The photoradical polymerization initiator can be used alone or in combination of two or more.

[0171] Examples of the photoradical polymerization initiator include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, and anthracene compounds.

[0172] Examples of the thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0173] Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzoin dimethyl ether, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-(2-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, and 2-(4-methylthiophenyl)-2-methylpropane-1-one. )-butanone, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-ethylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-propylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-butylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2,3-dimethylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2,4-dimethylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-chlorobenzyl)- 2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-chlorobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-chlorobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2 -(3-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-methyl-4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-bromo-4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, and the like.

[0174] Examples of the biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, and imidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carbonyl alkoxy groups.

[0175] Examples of the triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine. -[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

[0176] Examples of the oxime compound include O-ethoxycarbonyl-α-oxyimino-1-phenylpropane-1-one and the like.

[0177] Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0178] Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3′,4,4′-tetrakis(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone.

[0179] Examples of the anthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene.

[0180] The photocationic polymerization initiator is a compound that generates an acid by irradiation with light and initiates a curing reaction (cationic polymerization) of the photopolymerizable compound contained in the curable resin composition, and is composed of a cationic portion that absorbs light and an anionic portion that becomes a source of acid generation. The photocationic polymerization initiator can be used alone or in combination of two or more.

[0181] Examples of the photocationic polymerization initiator include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenonium salt compounds, oxonium salt compounds, ammonium salt compounds, and bromide salt compounds.

[0182] Examples of the anion portion of the photocationic polymerization initiator include: [(Y) s B(Phf) 4-s ] - (wherein, Y represents a phenyl group or a biphenyl group. Phf represents a phenyl group in which at least one of the hydrogen atoms is substituted by at least one selected from a perfluoroalkyl group, a perfluoroalkoxy group and a halogen atom. s is an integer of 0 to 3), BF 4 - 、[(Rf) k PF 6-k ] - (Rf: an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, k: an integer of 0 to 5), AsF 6 - , SbF 6 - , SbF 5 OH - wait.

[0183] Examples of the photocationic polymerization initiator include (4-hydroxyphenyl)methylbenzylsulfonium tetrakis(pentafluorophenyl)borate, 4-(4-biphenylthio)phenyl-4-biphenylphenylsulfonium tetrakis(pentafluorophenyl)borate, 4-(phenylthio)phenyldiphenylsulfoniumphenyl tris(pentafluorophenyl)borate, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfoniumphenyl tris(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate, and diphenyl [4-(phenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, 4-(4-biphenylthio)phenyl-4-biphenylphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, bis[4-(diphenylsulfonyl)phenyl]sulfidephenyl tris(pentafluorophenyl)borate, [4-(2-thioxanthonylthio)phenyl]phenyl-2-thioxanthonylsulfoniumphenyl tris(pentafluorophenyl)borate, 4-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate, and the like.

[0184] As the photocationic polymerization initiator, trade names "CYRACURE UVI-6970", "CYRACURE UVI-6974", "CYRACURE UVI-6990", "CYRACURE UVI-950" (all manufactured by Union Carbide, U.S.A.), "Irgacure 250", "Irgacure 261", "Irgacure 264" (all manufactured by BASF), "CG-24-61" (manufactured by Ciba Geigy), "OPTMER SP-150", "OPTMER SP-151", "OPTMER SP-170", "OPTMER SP-171" (all manufactured by ADEKA), "DAICAT II" (manufactured by Daicel Corporation), "UVAC1590", "UVAC1591" (manufactured by Daicel-Cytec Co., Ltd.), "CI-2064", "CI-2639", "CI-2624", "CI-2481", "CI-2734", "CI-2855", "CI-2823", "CI-2758", "CIT-1682" (manufactured by Nippon Soda Co., Ltd.), "PI-2074" (manufactured by Rhodia Co., Ltd., tetrakis(pentafluorophenyl)borate toluyl cumyl iodonium salt), "F Commercially available products include "FC509" (manufactured by 3M), "BBI-102", "BBI-101", "BBI-103", "MPI-103", "TPS-103", "MDS-103", "DTS-103", "NAT-103", "NDS-103" (all manufactured by Green Chemical Co., Ltd.), "CD-1010", "CD-1011", "CD-1012" (all manufactured by Sartomer, USA), "CPI-100P", "CPI-101A" (all manufactured by San-Apro), etc.

[0185] The content of the photopolymerization initiator (the total amount when two or more kinds are contained) is preferably, for example, 0.1 to 100 parts by weight, with a lower limit of 0.5 parts by weight and further preferably 3 parts by weight, relative to 100 parts by weight of the photopolymerizable compound (total amount) contained in the curable resin composition. In addition, the upper limit is more preferably 50 parts by weight and further preferably 20 parts by weight. When the content of the photopolymerization initiator is lower than the above range, there is a tendency for the curability to decrease. On the other hand, when the content of the photopolymerization initiator is higher than the above range, there is a tendency for the cured product to be easily colored.

[0186] <Solvent>

[0187] Examples of the solvent include ethers (ethyl ether; glycol ethers such as ethylene glycol mono- or dialkyl ethers, diethylene glycol mono- or dialkyl ethers, propylene glycol mono- or dialkyl ethers, propylene glycol mono- or diaryl ethers, dipropylene glycol mono- or dialkyl ethers, tripropylene glycol mono- or dialkyl ethers, 1,3-propylene glycol mono- or dialkyl ethers, 1,3-butanediol mono- or dialkyl ethers, 1,4-butanediol mono- or dialkyl ethers, glycerol mono-, di- or trialkyl ethers, etc.; chain ethers such as tetrahydrofuran, dimethicone ... alkyl and other cyclic ethers, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, C 5-6 Cycloalkyl glycol mono- or di-acetate, C 5-6 Cycloalkyl dimethanol mono- or di-acetate and other carboxylic acid esters; ethylene glycol mono-alkyl ether acetate, ethylene glycol mono- or di-acetate, diethylene glycol mono-alkyl ether acetate, diethylene glycol mono- or di-acetate, propylene glycol mono-alkyl ether acetate, propylene glycol mono- or di-acetate, dipropylene glycol mono-alkyl ether acetate, dipropylene glycol mono- or di-acetate, 1,3-propylene glycol mono-alkyl ether acetate, 1,3-propylene glycol mono- or di-acetate, 1,3-butylene glycol mono-alkyl ether acetate, 1,3-butylene glycol mono- or di-acetate, 1,4-butylene glycol mono-alkyl ether acetate, 1,4-butylene glycol mono- or di-acetate, glycerol mono-, di- or tri-acetate, glycerol mono- or di-C 1-4 Alkyl ether di- or monoacetate, tripropylene glycol monoalkyl ether acetate, tripropylene glycol mono- or diacetate, etc., glycol acetates or glycol ether acetates, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexene-1-one, etc.), etc. These solvents may be used alone or in combination of two or more.

[0188] In addition to the above-mentioned components, the curable resin composition of the present invention may also contain resins such as novolac resins, phenolic resins, imide resins, carboxyl-containing resins, curing agents, curing accelerators, additives (fillers, defoaming agents, flame retardants, antioxidants, ultraviolet absorbers, colorants (colorants), stress-reducing agents, flexibility-imparting agents, waxes, cross-linking agents, halogen scavengers, leveling agents, wetting improvers, etc.).

[0189] The content of the copolymer in the curable resin composition of the present disclosure is not particularly limited, and is, for example, 3 to 40% by weight. In addition, the content of the copolymer relative to the total amount of the curable compound contained in the curable resin composition is not particularly limited, and is, for example, preferably 20% by weight or more, more preferably 30% by weight or more, further preferably 40% by weight or more, and particularly preferably 50% by weight or more.

[0190] When the curable resin composition of the present disclosure contains a colorant, it can be used as a photosensitive resin composition. As a method for preparing the photosensitive resin composition, for example, a method of dispersing a colorant such as a pigment in a solvent to prepare a colorant dispersion, dissolving an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other additives used as necessary in a solvent, mixing the solvent with the colorant dispersion, and further adding a solvent as necessary can be cited.

[0191] The photosensitive resin composition of the present disclosure is usually sealed in a container and provided for distribution and storage. The photosensitive resin composition of the present disclosure has excellent storage stability during distribution and storage.

[0192] [cured material]

[0193] By curing the curable resin composition of the present disclosure, a cured product with excellent physical properties can be obtained. For example, after the curable resin composition is applied to various substrates or base plates by conventional coating means such as spin coating, dip coating, roll coating, slit coating, etc. to form a coating film, the coating film is cured to obtain a cured product. Curing can be performed, for example, by subjecting the curable resin composition to light irradiation and / or heat treatment.

[0194] The above-mentioned light irradiation can be carried out using, for example, a mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, sunlight, an electron beam source, a laser light source, an LED light source, etc., preferably with a cumulative irradiation amount of, for example, 500 to 5000 mJ / cm 2 range for irradiation.

[0195] The heat treatment is preferably performed at a temperature of, for example, 60 to 300° C. (preferably 100 to 250° C.) for, for example, 1 to 120 minutes (preferably 1 to 60 minutes).

[0196] Examples of the base material or substrate include silicon wafers, metals, plastics, glass, ceramics, etc. The thickness of the coating film after curing is, for example, preferably 0.05 to 20 μm, more preferably 0.1 to 10 μm.

[0197] The cured product (cured coating film) disclosed herein has excellent solvent resistance and high insulation properties, and is therefore useful as a protective film or insulating film, and is also useful as a material for forming a color filter protective film, a microlens, a coloring pattern, or the like, or a transparent film.

[0198] When the curable resin composition of the present disclosure contains a colorant, its cured product can be used as a color filter. The color filter may include a colored pattern formed by the photosensitive resin composition. The color filter may be manufactured, for example, by a process of forming a colored pattern on a substrate using the photosensitive resin composition and a process of post-baking the colored pattern.

[0199] Each method disclosed in this specification may also be combined with any other features disclosed in this specification. Each configuration and their combination in each embodiment is only an example, and the addition, omission, replacement and other changes of the configuration may be appropriately made within the scope of the subject matter of the present disclosure. In addition, each invention disclosed in this disclosure is not limited to the embodiment and the following examples, but only to the claims.

[0200] Example

[0201] Hereinafter, the present disclosure will be described in more detail based on examples, but the present disclosure is not limited to these examples.

[0202] The acid value of the copolymer was measured by neutralization titration using a 0.1N-NaOH standard solution. 0.5 g of the resin solution was accurately weighed, and 70 mL of THF and 10 mL of distilled water were added. 2 or 3 drops of phenolphthalein solution were added as an indicator, and the mixture was stirred to make it uniform. While stirring the solution, the mixture was titrated with a 0.1 mol / L NaOH aqueous solution, and the point at which the solution changed from colorless to pink was taken as the end point, and the acid value was calculated by the following formula.

[0203] Acid value (KOH mg / g) = A × F × 5.6 / S / non-volatile content (%) × 100

[0204] (where A is the amount (mL) of 0.1 mol / L NaOH aqueous solution added until the end point, F is the coefficient of 0.1N-NaOH aqueous solution, and S is the amount of sample collected (g))

[0205] [Production Example 1]

[0206] A 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer was purged with nitrogen gas to form a nitrogen atmosphere, 160 g of propylene glycol monomethyl ether acetate and 110 g of 1-methoxy 2-propanol were added, and the mixture was heated to 80°C while stirring. Then, a solution in which 254 g of 2-acryloyloxyethyl succinate and 76 g of 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M100) were dissolved in 180 g of propylene glycol monomethyl ether acetate as monomers, and a mixed solution in which 20 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 200 g of propylene glycol monomethyl ether acetate were added dropwise using a dropping pump over a period of about 5 hours. After the addition of the mixed solution was completed, the temperature was maintained for about 3 hours, and then cooled to room temperature to obtain a copolymer solution (C-1) having a solid content of 33.4% by weight. The weight average molecular weight Mw of the produced copolymer was 8100, the dispersion degree was 1.80, and the acid value was 200 KOHmg / g.

[0207] [Production Example 2]

[0208] A 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer was purged with nitrogen gas to form a nitrogen atmosphere, 145 g of propylene glycol monomethyl ether acetate and 110 g of 1-methoxy 2-propanol were added, and the mixture was heated to 80°C while stirring. Then, a solution in which 223 g of succinic acid 2-acryloyloxyethyl ester, 68 g of methacrylate 3,4-epoxycyclohexylmethyl ester (Cyclomer M100) and 38 g of styrene (ST) were dissolved in 180 g of propylene glycol monomethyl ether acetate as monomers, and a mixed solution in which 35 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 200 g of propylene glycol monomethyl ether acetate were added dropwise using a dropping pump over a period of about 5 hours. After the addition of the mixed solution was completed, the temperature was maintained for about 3 hours, and then cooled to room temperature to obtain a copolymer solution (C-2) having a solid content of 33.6% by weight. The weight average molecular weight Mw of the produced copolymer was 5500, the degree of dispersion was 1.67, and the acid value was 175 KOHmg / g.

[0209] [Production Example 3]

[0210] A nitrogen atmosphere was formed by passing an appropriate amount of nitrogen into a 1L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and propylene glycol monomethyl ether acetate 161g and 1-methoxy 2-propanol 110g were added, and heated to 80°C while stirring. Then, a solution in which 209g of succinic acid 2-acryloyloxyethyl ester, 63g of methacrylate 3,4-epoxycyclohexylmethyl ester (Cyclomer M100), and 58g of cyclohexylmaleimide (CHMI) were dissolved in 180g of propylene glycol monomethyl ether acetate as monomers, and a mixed solution in which 19g of 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 200g of propylene glycol monomethyl ether acetate were added dropwise using a dropping pump over a period of about 5 hours. After the addition of the mixed solution was completed, the temperature was maintained for about 3 hours, and then cooled to room temperature to obtain a copolymer solution (C-3) having a solid content of 33.4% by weight. The weight average molecular weight Mw of the produced copolymer was 8300, the degree of dispersion was 1.69, and the acid value was 165 KOHmg / g.

[0211] [Production Example 4]

[0212] A 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer was purged with nitrogen gas to form a nitrogen atmosphere, 168 g of propylene glycol monomethyl ether acetate and 110 g of 1-methoxy 2-propanol were added, and the mixture was heated to 80°C while stirring. Then, a solution of 138 g of 2-acryloyloxyethyl succinate, 98 g of 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M100) and 94 g of benzyl methacrylate (BzMA) dissolved in 180 g of propylene glycol monomethyl ether acetate as monomers, and a mixed solution of 12 g of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 200 g of propylene glycol monomethyl ether acetate were added dropwise using a dropping pump over about 5 hours. After the addition of the mixed solution was completed, the temperature was maintained for about 3 hours, and then cooled to room temperature to obtain a copolymer solution (C-4) having a solid content of 33.3% by weight. The weight average molecular weight Mw of the produced copolymer was 17100, the dispersion degree was 2.19, and the acid value was 108 KOHmg / g.

[0213] [Production Example 5]

[0214] A 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer was purged with an appropriate amount of nitrogen to form a nitrogen atmosphere, and 162 g of propylene glycol monomethyl ether acetate and 110 g of 1-methoxy 2-propanol were added, and heated to 80°C while stirring. Then, a solution in which 220 g of succinic acid 2-acryloyloxyethyl ester, 50 g of methacrylate 3,4-epoxycyclohexylmethyl ester (Cyclomer M100), and 60 g of butyl methacrylate (BMA) were dissolved in 180 g of propylene glycol monomethyl ether acetate as monomers, and a mixed solution in which 18 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 200 g of propylene glycol monomethyl ether acetate were added dropwise using a dropping pump over about 5 hours. After the addition of the mixed solution was completed, the temperature was maintained for about 3 hours, and then cooled to room temperature to obtain a copolymer solution (C-5) having a solid content of 33.7% by weight. The weight average molecular weight Mw of the produced copolymer was 9900, the degree of dispersion was 2.06, and the acid value was 173 KOHmg / g.

[0215] [Production Example 6]

[0216] A 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer was purged with nitrogen gas to form a nitrogen atmosphere, 95 g of propylene glycol monomethyl ether acetate and 220 g of 1-methoxy 2-propanol were added, and the mixture was heated to 65°C while stirring. Then, a solution in which 115 g of acrylic acid (AA) and 205 g of 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M100) as monomers were dissolved in 30 g of propylene glycol monomethyl ether acetate and 100 g of 1-methoxy 2-propanol, and a mixed solution in which 35 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 200 g of propylene glycol monomethyl ether acetate were added dropwise using a dropping pump over a period of about 5 hours. After the addition of the mixed solution was completed, the temperature was maintained for about 3 hours, and then cooled to room temperature to obtain a copolymer solution (C-6) having a solid content of 32.5% by weight. The weight average molecular weight Mw of the produced copolymer was 11,000, the dispersion degree was 3.51, and the acid value was 276.4 KOHmg / g.

[0217] [Production Example 7]

[0218] A 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer was purged with nitrogen gas to form a nitrogen atmosphere, 74 g of propylene glycol monomethyl ether acetate and 190 g of 1-methoxy 2-propanol were added, and the mixture was heated to 65°C while stirring. Then, a solution in which 101 g of acrylic acid (AA), 162 g of 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M100) and 57 g of styrene (ST) were dissolved in 130 g of 1-methoxy 2-propanol as monomers, and a mixed solution in which 36 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 250 g of propylene glycol monomethyl ether acetate were added dropwise using a dropping pump over a period of about 5 hours. After the addition of the mixed solution was completed, the temperature was maintained for about 3 hours, and then cooled to room temperature to obtain a copolymer solution (C-7) having a solid content of 32.4% by weight. The weight average molecular weight Mw of the produced copolymer was 9800, the dispersion degree was 3.36, and the acid value was 242.2 KOHmg / g.

[0219] [Production Example 8]

[0220] A 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer was purged with an appropriate amount of nitrogen gas to form a nitrogen atmosphere, and 8 g of propylene glycol monomethyl ether acetate and 210 g of 1-methoxy 2-propanol were added, and heated to 65° C. while stirring. Then, a solution prepared by dissolving 131 g of methacrylic acid (MAA), 99 g of 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M100) and 91 g of cyclohexylmaleimide (CHMI) as monomers in 60 g of propylene glycol monomethyl ether acetate and 110 g of 1-methoxy 2-propanol, and a mixed solution prepared by dissolving 42 g of 2,2′-azobis(2,4-dimethylvaleronitrile) in 250 g of propylene glycol monomethyl ether acetate were added dropwise using a dropping pump over about 5 hours. After the addition of the mixed solution was completed, the temperature was maintained for about 3 hours and then cooled to room temperature to obtain a copolymer solution (C-8) with a solid content of 32.3% by weight. The weight average molecular weight Mw of the generated copolymer was 7500, the dispersity was 2.21, and the acid value was 266.3 KOHmg / g.

[0221] [Production Example 9]

[0222] A 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer was purged with an appropriate amount of nitrogen to form a nitrogen atmosphere, and 60 g of propylene glycol monomethyl ether acetate and 170 g of 1-methoxy 2-propanol were added, and heated to 65°C while stirring. Then, a solution in which 104 g of methacrylic acid (MAA), 157 g of 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M100) and 89 g of benzyl methacrylate (BzMA) were dissolved in 140 g of 1-methoxy 2-propanol as monomers, and a mixed solution in which 30 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 250 g of propylene glycol monomethyl ether acetate were added dropwise using a dropping pump over about 5 hours. After the addition of the mixed solution was completed, the temperature was maintained for about 3 hours, and then cooled to room temperature to obtain a copolymer solution (C-9) having a solid content of 35.8% by weight. The weight average molecular weight Mw of the produced copolymer was 8400, the degree of dispersion was 2.15, and the acid value was 193.9 KOHmg / g.

[0223] [Production Example 10]

[0224] A 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer was purged with nitrogen gas to form a nitrogen atmosphere, and 64 g of propylene glycol monomethyl ether acetate and 190 g of 1-methoxy 2-propanol were added, and the mixture was heated to 65°C while stirring. Then, a solution in which 122 g of acrylic acid (AA), 109 g of 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M100) and 79 g of butyl methacrylate (BMA) were dissolved in 130 g of 1-methoxy 2-propanol as monomers, and a mixed solution in which 46 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 260 g of propylene glycol monomethyl ether acetate were added dropwise using a dropping pump over a period of about 5 hours. After the addition of the mixed solution was completed, the temperature was maintained for about 3 hours, and then cooled to room temperature to obtain a copolymer solution (C-10) having a solid content of 31.4% by weight. The weight average molecular weight Mw of the produced copolymer was 10700, the degree of dispersion was 3.20, and the acid value was 302.7 KOHmg / g.

[0225] [Example 1]

[0226] 78 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of p-hydroxyanisole were added to the copolymer solution (C-1) obtained in Production Example 1, and the mixture was reacted at 90° C. for 13 hours to obtain a copolymer solution (P-1). The reaction was carried out in a mixed gas stream of 6% oxygen and 94% nitrogen by volume.

[0227] [Example 2]

[0228] A copolymer solution (P-2) was obtained by the same method as in Example 1 except that 55 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of p-hydroxyanisole were added to the copolymer solution (C-2) obtained in Production Example 2.

[0229] [Example 3]

[0230] A copolymer solution (P-3) was obtained by the same method as in Example 1 except that 69 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of p-hydroxyanisole were added to the copolymer solution (C-3) obtained in Production Example 3.

[0231] [Example 4]

[0232] A copolymer solution (P-4) was obtained by the same method as in Example 1 except that 43 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of p-hydroxyanisole were added to the copolymer solution (C-4) obtained in Production Example 4.

[0233] [Example 5]

[0234] A copolymer solution (P-5) was obtained by the same method as in Example 1 except that 72 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of p-hydroxyanisole were added to the copolymer solution (C-5) obtained in Production Example 5.

[0235] [Comparative Example 1]

[0236] A copolymer solution (P-6) was obtained by the same method as in Example 1 except that 112 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of p-hydroxyanisole were added to the copolymer solution (C-6) obtained in Production Example 6.

[0237] [Comparative Example 2]

[0238] A copolymer solution (P-7) was obtained by the same method as in Example 1 except that 98 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of p-hydroxyanisole were added to the copolymer solution (C-7) obtained in Production Example 7.

[0239] [Comparative Example 3]

[0240] A copolymer solution (P-8) was obtained by the same method as in Example 1 except that 108 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of p-hydroxyanisole were added to the copolymer solution (C-8) obtained in Production Example 8.

[0241] [Comparative Example 4]

[0242] A copolymer solution (P-9) was obtained by the same method as in Example 1 except that 64 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of p-hydroxyanisole were added to the copolymer solution (C-9) obtained in Production Example 9.

[0243] [Comparative Example 5]

[0244] A copolymer solution (P-10) was obtained by the same method as in Example 1 except that 127 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of p-hydroxyanisole were added to the copolymer solution (C-10) obtained in Production Example 10.

[0245] The copolymer compositions of the copolymer solutions (P-1) to (P-10) obtained in Examples 1 to 5 and Comparative Examples 1 to 5 are shown in Table 1. It should be noted that the molar ratio (mol %) of the structural units is recorded as the ratio of the amounts of the corresponding compounds. Among them, the structural units (A) and (C) were calculated as follows.

[0246] The molar ratio of the structural unit (A) is calculated by subtracting the amount of the polymerizable unsaturated compound (c) containing an epoxy group from the amount of the compound (a) represented by the formula (1). It is assumed that all of the polymerizable unsaturated compound (c) containing an epoxy group used has reacted with the carboxyl group of the compound (a) represented by the formula (1). The molar ratio of the structural unit (C) is the molar ratio of the polymerizable unsaturated compound (c) containing an epoxy group used.

[0247] The following evaluation tests were performed using the copolymer solutions (P-1) to (P-10) obtained in Examples 1 to 5 and Comparative Examples 1 to 5. The results are shown in Table 1.

[0248] (Manufacturing stability test)

[0249] In Examples 1 to 5 and Comparative Examples 1 to 5, the copolymer solution after the reaction was gelled, which was recorded as "gelled" in Table 1. In addition, the weight average molecular weight (in terms of polystyrene) of the copolymer solution obtained was measured, and the manufacturing stability was evaluated based on the value of the molecular weight distribution. In Table 1, the case where the molecular weight distribution is 2.5 or less is recorded as "◎", the case where it exceeds 2.5 and is 3.5 or less is recorded as "○", and the case where it exceeds 3.5 is recorded as "△".

[0250] (Storage stability test)

[0251] The weight average molecular weight (in terms of polystyrene) of the copolymer solutions obtained in Examples 1 to 5 and Comparative Examples 1 to 5 was measured, and the weight average molecular weight was measured after being stored in an oven at 40°C for 2 weeks. The increase rate of the weight average molecular weight during this period was calculated using the following calculation formula, and the results are recorded in Table 1.

[0252] P: weight average molecular weight before storage (immediately after synthesis), Q: weight average molecular weight after storage

[0253] Weight average molecular weight increase rate (%) = {(Q / P) × 100} - 100

[0254] The weight average molecular weight (in terms of polystyrene) and molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of the copolymer were measured using the following apparatus.

[0255] Device: Detector: RID-20A (Shimadzu Corporation)

[0256] Pump: LC-20AD (Shimadzu Corporation)

[0257] System controller: CBM-20Alite (Shimadzu Corporation)

[0258] Degasser: DGU-20A3 (Shimadzu Corporation)

[0259] Automatic sample injector: SIL-20A HT (Shimadzu Corporation)

[0260] Column: Shodex KF-806L (Showa Denko)

[0261] Eluent: THF (tetrahydrofuran) 0.8 ml / min

[0262] Temperature: Oven: 40℃, RI: 40℃

[0263] Detector: RI

[0264]

[0265] The copolymers of Examples 1 to 5 showed excellent manufacturing stability and excellent storage stability because the weight average molecular weight was not easily increased even at 40°C. On the other hand, the copolymers of Comparative Examples 1, 2 and 5 showed that gelation occurred during manufacturing and the manufacturing stability was poor. In addition, the copolymers of Comparative Examples 3 and 4 showed that the weight average molecular weight increased over time at 40°C and the storage stability was insufficient. As one of the reasons for this, it can be cited that the copolymers of Examples 1 to 5 have structural units derived from 2-acryloyloxyethyl succinate, while the copolymers of Comparative Examples 1 to 5 do not have the above structural units. Specifically, since the side chain of the structural unit derived from 2-acryloyloxyethyl succinate contains an ester bond and has a certain degree of length, the acidity of the copolymer as a whole is moderately reduced. Therefore, it can be considered that during the manufacture of the copolymer, the reactivity of the epoxy group of the copolymer, i.e., the alicyclic epoxy group derived from Cyclomer M100, is reduced, and therefore, the epoxy group derived from glycidyl methacrylate (GMA) preferentially reacts with the carboxyl group derived from 2-acryloyloxyethyl succinate, and thus gelation is not likely to occur. In addition, it can be considered that after manufacture, the reaction between the carboxyl group and the epoxy group in the molecule of the copolymer is not likely to occur, and therefore, no increase in the weight average molecular weight over time is observed.

[0266] [Examples 6 to 10 and Comparative Examples 6 to 7]

[0267] Curable resin compositions were prepared by mixing given components at the ratios described in Table 2, and the following evaluations were performed. The results are shown in Table 2. In addition, the units of the components of the curable resin compositions in the table are parts by weight.

[0268] (Solvent resistance test)

[0269] The curable resin composition obtained in Examples 6 to 10 and Comparative Examples 6 to 7 was applied to a glass plate using a spin coater, and then pre-baked at 80°C for 3 minutes to form a coating film with a film thickness of about 5 μm. The resulting coating film was cured at 500 W for 60 seconds using a high-pressure mercury lamp, and then heated and cured at 180°C for 15 minutes, thereby preparing each evaluation test piece. Furthermore, each evaluation test piece was prepared by the same method except that 180°C was changed to 230°C.

[0270] One drop of N-methylpyrrolidone (NMP) and one drop of γ-butyrolactone (γ-BL) were added to the test piece for evaluation, and the test piece was left for 10 minutes. Then, the test piece was washed with water, and the case where the part where the solvent was added was completely unchanged was marked as ◎, the case where a small amount of solvent remained was marked as ○, the case where partial discoloration and swelling occurred was marked as △, and the case where the entire surface was discolored and dissolved was marked as ×.

[0271]

[0272] The curable resin compositions of Examples 6 to 10 showed good solvent resistance even at a curing temperature of 180° C., similar to the case of 230° C. On the other hand, the curable resin compositions of Comparative Examples 6 and 7 showed poor solvent resistance.

[0273] Hereinafter, the components used in Tables 1 and 2 will be described.

[0274] AES: 2-Acryloyloxyethyl succinate (manufactured by Kyoeisha Chemical Co., Ltd.)

[0275] AA: Acrylic acid (manufactured by Mitsubishi Chemical Corporation)

[0276] MAA: methacrylic acid (manufactured by Mitsubishi Chemical Corporation)

[0277] M100: 3,4-epoxycyclohexylmethyl methacrylate (trade name "Cyclomer M100", manufactured by Daicel Corporation)

[0278] GMA: Glycidyl methacrylate (manufactured by NOF Corporation)

[0279] ST: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0280] CHMI: N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.)

[0281] BzMA: Benzyl methacrylate (manufactured by Mitsubishi Chemical Corporation)

[0282] BMA: Butyl methacrylate (manufactured by Mitsubishi Chemical Corporation)

[0283] DPHA: dipentaerythritol hexaacrylate (manufactured by DAICEL-ALLNEX)

[0284] IRG184: 1-Hydroxycyclohexylphenylketone (manufactured by BASF JAPAN)

[0285] PEMP: Pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by Showa Denko K.K.)

[0286] MMPGAc: Propylene glycol monomethyl ether acetate (manufactured by Daicel Corporation)

[0287] As a summary of the above, the configuration of the present disclosure and its modifications are described below.

[0288] [1] A copolymer comprising:

[0289] From the above formula (1) (wherein, R 1a represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. 2a represents a divalent organic group. a represents a hetero atom. The structural unit (A) of the compound (a) represented by

[0290] The structural unit (B) derived from the polymerizable unsaturated compound (b) containing an epoxy group, and

[0291] The structural unit (C) derived from an addition reaction product of the compound (a) represented by the above formula (1) and the polymerizable unsaturated compound (c) containing an epoxy group,

[0292] The copolymer has:

[0293] derived from the carboxyl group of the compound (a) represented by the above formula (1),

[0294] The epoxy group derived from the above-mentioned epoxy group-containing polymerizable unsaturated compound (b), and

[0295] A polymerizable unsaturated group derived from the above-mentioned epoxy group-containing polymerizable unsaturated compound (c).

[0296] [2] The copolymer according to [1], which is obtained by subjecting a copolymer containing the structural unit (A) and the structural unit (B) to an addition reaction with the compound (c).

[0297] [3] The copolymer according to [1] or [2], wherein in the compound (a), R 1a Represents a hydrogen atom.

[0298] [4] The copolymer according to any one of [1] to [3], wherein in the compound (a), R of the formula (1) 2a It represents a divalent organic group including an ester bond.

[0299] [5] The copolymer according to any one of [1] to [4], wherein in the compound (a), R of the formula (1) 2a represents a group formed by two alkylene groups bonded via a linking group, a group formed by two alkylene groups bonded via an ester bond, or -C 2 H 4 -O-(C=O)-C 2 H 4 -Base (from the left side of C 2 H 4 The bond arm extending to the left of the base and the X a Bonding, from the right side of C 2 H 4 The bond arm extending to the right of the (C=O)-OH group is bonded to the carbon atom of the (C=O)-OH group).

[0300] [6] The copolymer according to any one of [1] to [5], wherein in the compound (a), X of the formula (1) a The hetero atom in represents a nitrogen atom, an oxygen atom or a sulfur atom.

[0301] [7] The copolymer according to any one of [1] to [6], wherein the proportion of the structural unit (A) in the copolymer is 10 to 50 mol% with a lower limit of 20 mol% and an upper limit of 40 mol% relative to all the structural units constituting the copolymer.

[0302] [8] The copolymer according to any one of [1] to [7], wherein the epoxy group of the compound (b) is an alicyclic epoxy group.

[0303] [9] The copolymer according to any one of [1] to [8], wherein the epoxy group of the compound (b) is a monocyclic or bicyclic alicyclic epoxy group.

[0304]

[10] The copolymer according to any one of [1] to [9], wherein the compound (b) is of the formula (2) (wherein R1b represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. 2b are the same or different and represent an alkyl group having 1 to 7 carbon atoms. b represents a single bond or a divalent organic group. 2b The substituents on the cyclohexane ring shown in formula (2) are not included in Y b Substituents possessed by Y b Indicates non-bonding (meaning there is no b A compound represented by: a group corresponding to a carbon atom, a methylene group or an ethylene group optionally having an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom optionally bonded to an oxygen atom. n represents an integer greater than 0 (preferably an integer from 0 to 7).

[0305]

[11] The copolymer according to any one of [1] to

[10] , wherein the compound (b) is of the formula (2′) (wherein R 1b represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. 2b are the same or different and represent an alkyl group having 1 to 7 carbon atoms. b represents a single bond or a divalent organic group. 2b The substituents on the cyclohexane ring shown in formula (2') are not included in Y b Substituents possessed by Y b Indicates non-bonding (meaning there is no b A compound represented by: a group corresponding to a carbon atom, a methylene group or an ethylene group optionally having an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom optionally bonded to an oxygen atom. n represents an integer greater than 0 (preferably an integer from 0 to 7).

[0306]

[12] The copolymer according to

[10] or

[11] , wherein X in the formula (2) or (2′) in the compound (b) is b represents a divalent organic group (preferably an alkylene group such as methylene) or Y b Is non-bonded.

[0307]

[13] A copolymer according to any one of [1] to

[12] , wherein the proportion of the structural unit (B) in the copolymer is 5 to 40 mol% relative to all the structural units constituting the copolymer, with a lower limit of 10 mol% or 15 mol% and an upper limit of 35 mol% or 30 mol%.

[0308]

[14] The copolymer according to any one of [1] to

[13] , wherein the compound (c) is different from the compound (b).

[0309]

[15] The copolymer according to any one of [1] to

[14] , wherein in the compound (c), the epoxy group is a group bonded to an aliphatic hydrocarbon group (aliphatic epoxy group), preferably a glycidyl group.

[0310]

[16] The copolymer according to any one of [1] to

[15] , wherein the compound (c) is at least one selected from allyl glycidyl ether, glycidyl (meth)acrylate, 2-methyl glycidyl (meth)acrylate, 2-ethyl glycidyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxypropyl (meth)acrylate, glycidyloxyphenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate glycidyl ether, and 4-hydroxybutyl (meth)acrylate glycidyl ether.

[0311]

[17] A copolymer according to any one of [1] to

[16] , wherein the proportion of the structural unit (C) in the copolymer is 10 to 60 mol% relative to all the structural units constituting the copolymer, with a lower limit of 15 mol%, or an upper limit of 50 mol% or 35 mol%.

[0312]

[18] The copolymer according to any one of [1] to

[17] , further comprising a structural unit (D) derived from at least one compound selected from the following (d1) to (d4).

[0313] (d1) Styrene optionally substituted with an alkyl group

[0314] (d2) N-substituted maleimide

[0315] (d3) N-vinyl compounds

[0316] (d4) the above formula (4) (wherein, R 1d represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. 2d represents a monovalent organic group. d represents a hetero atom. Unsaturated carboxylic acid derivative represented by

[0317]

[19] The copolymer according to

[18] , which is obtained by subjecting a copolymer comprising the structural unit (A), the structural unit (B) and the structural unit (D) to an addition reaction with the compound (c).

[0318]

[20] The copolymer according to

[18] or

[19] , wherein the proportion of the structural unit (D) in the copolymer is 0 to 50 mol% relative to all the structural units constituting the copolymer, with a lower limit of 1 mol% and an upper limit of 35 mol%.

[0319]

[21] The copolymer according to any one of [1] to

[20] , wherein, when the copolymer contains the structural unit (A), the structural unit (B) and the structural unit (C) but does not contain the structural unit (D), the total amount of the structural units (A) to (C) is 90 mol% or more, 95 mol% or more, 99 mol% or more, or substantially 100 mol% relative to all the structural units constituting the copolymer; and when the copolymer contains the structural unit (A), the structural unit (B), the structural unit (C) and the structural unit (D), the total amount of the structural units (A) to (D) is 90 mol% or more, 95 mol% or more, 99 mol% or more, or substantially 100 mol% relative to all the structural units constituting the copolymer.

[0320]

[22] The copolymer according to any one of [1] to

[21] , wherein the weight average molecular weight (Mw) is 5,000 to 70,000 or 7,000 to 20,000, and the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight: Mw / Mn) is 3.5 or less (e.g., 1.1 to 3.5) or 2.5 or less (1.1 to 2.5).

[0321]

[23] The copolymer according to any one of [1] to

[22] , wherein the acid value is 30 to 120 mgKOH / g or 40 to 100 mgKOH / g.

[0322]

[24] A curable resin composition comprising the copolymer according to any one of [1] to

[23] .

[0323]

[25] The curable resin composition comprising a copolymer according to

[24] , further comprising a polyfunctional vinyl compound, a polyfunctional thiol compound or a polyfunctional epoxy compound.

[0324]

[26] The curable resin composition according to

[24] or

[25] , further comprising a photopolymerization initiator.

[0325]

[27] The curable resin composition according to any one of

[24] to

[26] , further comprising a colorant.

[0326]

[28] A curable resin composition according to any one of

[24] to

[27] , wherein the content of the copolymer in the curable resin composition is 3 to 40 weight %, and the content of the copolymer is 20 weight % or more, 30 weight % or more, 40 weight % or more, or 50 weight % or more relative to the total amount of curable compounds contained in the curable resin composition.

[0327]

[29] A cured product, which is a cured product of the curable resin composition according to any one of

[24] to

[28] .

[0328]

[30] A color filter which is a cured product of the curable resin composition according to any one of

[24] to

[28] .

[0329]

[31] A method for producing a copolymer, the method comprising:

[0330] In the above formula (1) (wherein, R 1a represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. 2a represents a divalent organic group. a represents a hetero atom. After copolymerization of the compound (a) represented by (a) and the epoxy group-containing polymerizable unsaturated compound (b), the epoxy group of the epoxy group-containing polymerizable unsaturated compound (c) is added to part of the carboxyl groups of the obtained copolymer.

[0331] Industrial Applicability

[0332] The copolymer disclosed herein has excellent curability, manufacturing stability and storage stability, and can impart excellent solvent resistance to a cured product. In addition, a curable resin composition containing the copolymer has excellent curability. In addition, its cured product has excellent solvent resistance.

Claims

1. A copolymer comprising: The structural unit (A) derived from the compound (a) represented by the following formula (1), The structural unit (B) derived from the polymerizable unsaturated compound (b) containing an epoxy group, and A structural unit (C) derived from an addition reaction product of the compound (a) represented by the formula (1) and an epoxy group-containing polymerizable unsaturated compound (c), In formula (1), R 1a represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, R 2a represents a divalent organic group, X a represents a heteroatom, The copolymer has: derived from the carboxyl group of the compound (a) represented by the formula (1), An epoxy group derived from the epoxy group-containing polymerizable unsaturated compound (b), and The polymerizable unsaturated group is derived from the polymerizable unsaturated compound (c) containing an epoxy group.

2. The copolymer according to claim 1, wherein The epoxy group of the compound (b) is an alicyclic epoxy group.

3. The copolymer according to claim 1 or 2, wherein The epoxy group of the compound (b) is a monocyclic or bicyclic alicyclic epoxy group.

4. The copolymer according to claim 1 or 2, wherein In the compound (c), an epoxy group and an aliphatic hydrocarbon group are bonded together.

5. The copolymer according to claim 1 or 2, wherein In the compound (a), R of formula (1) 2a It represents a divalent organic group including an ester bond.

6. The copolymer according to claim 1 or 2, further comprising a structural unit (D) derived from at least one compound selected from the following (d1) to (d4): (d1) styrene optionally substituted with an alkyl group, (d2) N-substituted maleimide, (d3) N-vinyl compounds, (d4) an unsaturated carboxylic acid derivative represented by the following formula (4), In formula (4), R 1d represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, R 2d represents a monovalent organic group, X d Represents a heteroatom. 7 . A curable resin composition comprising the copolymer according to claim 1 . The curable resin composition according to claim 7 , further comprising a photopolymerization initiator. 9 . The curable resin composition according to claim 7 , further comprising a colorant. 10 . A cured product, which is a cured product of the curable resin composition according to claim 7 . 11 . A color filter which is a cured product of the curable resin composition according to claim 9 .

12. A method for producing a copolymer, the method comprising: After copolymerizing a compound (a) represented by the following formula (1) and an epoxy group-containing polymerizable unsaturated compound (b), an epoxy group of the epoxy group-containing polymerizable unsaturated compound (c) is added to part of the carboxyl groups of the obtained copolymer. In formula (1), R 1a represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, R 2a represents a divalent organic group, X a Represents a heteroatom.

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