TW202216812A - Copolymer, copolymer solution, photosensitive resin composition, cured article, method for producing copolymer, and method for producing copolymer solution - Google Patents

Abstract

The purpose of the present invention is to provide a copolymer which can provide a cured article having excellent solvent resistance under low-temperature curing conditions and can be used suitably as a heat-curable resin in various use applications including a color filter. The present invention is a copolymer characterized by comprising (A) an epoxy-group-containing structural unit represented by general formula (1) and (B) an acidic-group-containing structural unit represented by general formula (2), and also characterized in that the epoxy equivalent is 20000 or less. (In formula (1), R1 represents a hydrogen atom or a methyl group; R2 represents a direct bond or a bivalent organic group; and X represents an epoxy-group-containing group.) (In formula (2), R3 represents a hydrogen atom or a methyl group; R4 represents a direct bond or an organic group; R5 represents a bond chain having a length of 2 atoms or more; Y represents an acidic group; and a represents 0 or 1.).

Description

Copolymer, copolymer solution, photosensitive resin composition, cured product, method for producing copolymer, and method for producing copolymer solution

The present invention relates to a copolymer. More specifically, the present invention relates to a copolymer, a copolymer solution, a photosensitive resin composition, a cured product, a method for producing the copolymer that can form a cured product excellent in solvent resistance even under low-temperature curing conditions, and A method for producing a copolymer solution.

For compositions containing curable resins, for example, color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, organic insulating films, organic Various studies have been carried out on the application of various optical members such as protective films to various applications such as electrical and electronic equipment, and resins or resin compositions with excellent properties required for each application have been developed. In recent years, with the progress of miniaturization, thinning, and energy saving of optical components, motors, and electronic devices, higher-quality performance is expected for various components used. In order to meet this demand, research is being conducted on curable resins as materials for various members and the like.

So far, curable resins corresponding to various requirements have been developed. For example, Patent Document 1 describes a photosensitive resin composition containing an oligomer having a carboxyl group and a photoreactive unsaturated group in its side chain and soluble in an alkaline aqueous solution, a compound having an epoxy group, an Sensitizers, and dicyandiamine modifiers. Moreover, for example, Patent Document 2 describes a photosensitive composition containing a radically polymerizable monomer having an epoxy group or an oxetanyl group, a radically polymerizable monomer having a carboxyl group, and the like Alkali-soluble polymer obtained by polymerization. In addition, for example, Patent Document 3 describes a curable polymer and a photosensitive polymer composition containing the curable polymer, wherein the curable polymer is prepared as a homopolymer with a glass transition temperature of 10 The addition copolymers of (meth)acrylate monomers below °C, (meth)acrylate monomers having epoxy groups or carboxyl groups, etc. are subjected to specific modification reactions to obtain acid groups and hydroxyl groups in the side chain. and polymeric unsaturated bonds. prior art literature Patent Literature

Patent Document 1: Japanese Patent Application Laid-Open No. 4-25846 Patent Document 2: Japanese Patent Laid-Open No. 2006-251009 Patent Document 3: Japanese Patent Laid-Open No. 2014-210892

[The problem to be solved by the invention]

As described above, various studies have been conducted on curable resins so far. If conventional curable resins and colorants are used as raw materials for, for example, color filters, the colorants exist in the manufacturing process of color filters. The problem of elution from the raw material into the cleaning solvent. Therefore, further improvement of the solvent resistance of the curable resin is required.

In addition, in recent years, especially in the use of color filters, with the improvement of the quality of color liquid crystal display devices and the expansion of applications, the industry has strongly demanded higher performances such as high brightness and high contrast of display panels. However, in the manufacturing process of the color filter, there is a problem in that if the baking treatment step (post-curing step) is performed at a high temperature exceeding 200° C. after exposure and development, the obtained cured product will be yellowed, etc. discoloration, and the high coloration with the desired color cannot be fully performed. In addition, there is also a problem that when the baking treatment step is performed at a high temperature, a useless reaction proceeds to generate by-products, and the properties of the base material or the cured film are degraded. In order to suppress such a useless reaction and efficiently obtain a color filter having desired characteristics, it is desirable that the curing reaction sufficiently proceeds even under heating conditions at a relatively low temperature of 200°C or lower. Moreover, if the curable resin composition can be hardened at a relatively low temperature, the manufacturing efficiency of a color filter can also be improved. The conventional photosensitive resin composition described in Patent Document 1 requires a relatively high temperature for resin synthesis. In addition, there is room for improvement in the curability of the resin.

The present invention has been made in view of the above-mentioned situation, and an object of the present invention is to provide a cured product excellent in solvent resistance even under low-temperature curing conditions, which can be preferably used as a thermosetting resin in various applications such as color filters. the copolymer. [Technical means to solve the problem]

The inventors of the present invention have conducted various studies on curable resins, and as a result found that, by preparing a copolymer having an epoxy group-containing group and a long-chain acid group in one molecule and having an epoxy equivalent in a specific range, even at 160° C. Under the following low-temperature curing conditions, the crosslinking reaction proceeds well, and a cured product excellent in solvent resistance can be formed, thereby completing the present invention.

That is, the present invention is a copolymer having an epoxy group-containing structural unit (A) represented by the following general formula (1), and an acid group-containing structural unit (A) represented by the following general formula (2). B), and the epoxy equivalent is 20,000 or less.

（式（1）中，R ¹表示氫原子或甲基；R ²表示直接鍵結或二價有機基；X表示含環氧基之基）。

(In formula (1), R ¹ represents a hydrogen atom or a methyl group; R ² represents a direct bond or a divalent organic group; X represents a group containing an epoxy group).

(In formula (2), R ³ represents a hydrogen atom or a methyl group; R ⁴ represents a direct bond or an organic group; R ⁵ represents a bond chain with a length of 2 atoms or more; Y represents an acid group; a represents 0 or 1 ).

In the above-mentioned copolymer, the above-mentioned structural unit (A) preferably contains a structural unit represented by the following general formula (1-1).

（式（1-1）中，R ¹表示氫原子或甲基；R ⁶表示直接鍵結或二價有機基）。

(In formula (1-1), R ¹ represents a hydrogen atom or a methyl group; R ⁶ represents a direct bond or a divalent organic group).

In the above-mentioned copolymer, the above-mentioned structural unit (B) preferably contains a structural unit represented by the following general formula (2-1).

（式（2-1）中，R ³表示氫原子或甲基；R ⁷及R ⁸相同或不同，表示直接鍵結或有機基；b表示0或1）。

(In formula (2-1), R ³ represents a hydrogen atom or a methyl group; R ⁷ and R ⁸ are the same or different, and represent a direct bond or an organic group; b represents 0 or 1).

The above-mentioned copolymer is preferably a copolymer further having a ring structure in the main chain.

The above-mentioned copolymer preferably further contains a structural unit derived from a monomer having 5 to 20 atoms in the longest side chain or a monomer having a ring structure in the side chain.

The present invention is also a copolymer solution characterized by containing the above-mentioned copolymer and a protic polar solvent.

It is preferable that the said copolymer solution further contains the acid compound whose pKa is 4.2 or less.

It is preferable that the said copolymer solution further contains a phosphoric acid derivative.

It is preferable that the said copolymer solution further contains a basic compound.

Moreover, this invention is also a photosensitive resin composition characterized by containing the said copolymer or a copolymer solution, a polymerizable compound, and a photopolymerization initiator.

It is preferable that the said photosensitive resin composition further contains a coloring material.

It is preferable that the said photosensitive resin composition is a negative type.

Moreover, this invention is also the hardened|cured material of the hardened|cured material of the said copolymer, the hardened|cured material of the said copolymer solution, or the hardened|cured material of the said photosensitive resin composition.

Furthermore, the present invention is also a method for producing a copolymer, characterized by comprising: mixing an epoxy group-containing monomer represented by the following formula (a) and a hydroxyl group-containing monomer represented by the following formula (b1). A step of polymerizing the monomer components of the monomer; and a step of reacting the polymer obtained in the above-mentioned polymerization step with an acid group-containing compound represented by the following formula (b2) or formula (b3).

（式（a）中，R ¹表示氫原子或甲基；R ²表示直接鍵結或二價有機基；X表示含環氧基之基）。

(In formula (a), R ¹ represents a hydrogen atom or a methyl group; R ² represents a direct bond or a divalent organic group; X represents a group containing an epoxy group).

（式（b1）中，R ³表示氫原子或甲基；R ⁴表示直接鍵結或有機基）。

(In formula (b1), R ³ represents a hydrogen atom or a methyl group; R ⁴ represents a direct bond or an organic group).

（式（b2）中，R ⁵表示長度為2個原子以上之鍵結鏈；Y表示酸基）。

(In formula (b2), R ⁵ represents a bond chain with a length of 2 atoms or more; Y represents an acid group).

（式（b3）中，R ⁵表示長度為2個原子以上之鍵結鏈）。

(In formula (b3), R ⁵ represents a bond chain having a length of 2 atoms or more).

Furthermore, the present invention is also a method for producing a copolymer solution, characterized by comprising: adding an epoxy group-containing monomer represented by the following formula (a) and a hydroxyl group-containing monomer represented by the following formula (b1). The step of polymerizing the monomer components of the monomer; the polymer obtained in the above-mentioned polymerization step is reacted with the acid group-containing compound represented by the following formula (b2) or formula (b3) in the presence of a basic compound and the step of adding an acid compound with a pKa of 4.2 or less and a protic polar solvent.

（式（a）中，R ¹表示氫原子或甲基；R ²表示直接鍵結或二價有機基；X表示含環氧基之基）。

(In formula (a), R ¹ represents a hydrogen atom or a methyl group; R ² represents a direct bond or a divalent organic group; X represents a group containing an epoxy group).

（式（b1）中，R ³表示氫原子或甲基；R ⁴表示直接鍵結或有機基）。

(In formula (b1), R ³ represents a hydrogen atom or a methyl group; R ⁴ represents a direct bond or an organic group).

（式（b2）中，R ⁵表示長度為2個原子以上之鍵結鏈；Y表示酸基）。

(In formula (b2), R ⁵ represents a bond chain with a length of 2 atoms or more; Y represents an acid group).

（式（b3）中，R ⁵表示長度為2個原子以上之鍵結鏈）。 [發明之效果]

(In formula (b3), R ⁵ represents a bond chain having a length of 2 atoms or more). [Effect of invention]

The copolymer of the present invention can form a cured product with excellent solvent resistance even under a relatively low temperature curing condition below 160°C. The copolymer of the present invention can be preferably used for the constitution of various optical components, motors, and electronic devices used in liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state imaging devices, touch panel display devices, etc. components, etc.

Hereinafter, the present invention will be described in detail. In addition, what combined 2 or more of each preferable aspect of this invention described below is also a preferable aspect of this invention. In addition, in this specification, "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid", and "(meth)acrylate" means "acrylate and/or methacrylate".

1. Copolymer The copolymer of the present invention is characterized by having an epoxy group-containing structural unit (A) represented by the following general formula (1) and an acid group-containing structural unit (B) represented by the following general formula (2). ), and the epoxy equivalent is 20,000 or less.

（式（1）中，R ¹表示氫原子或甲基；R ²表示直接鍵結或二價有機基；X表示含環氧基之基）。

(In formula (1), R ¹ represents a hydrogen atom or a methyl group; R ² represents a direct bond or a divalent organic group; X represents a group containing an epoxy group).

（式（2）中，R ³表示氫原子或甲基；R ⁴表示直接鍵結或有機基；R ⁵表示長度為2個原子以上之鍵結鏈；Y表示酸基；a表示0或1）。

(In formula (2), R ³ represents a hydrogen atom or a methyl group; R ⁴ represents a direct bond or an organic group; R ⁵ represents a bond chain with a length of 2 atoms or more; Y represents an acid group; a represents 0 or 1 ).

It is presumed that the copolymer of the present invention can form a cured product with excellent solvent resistance even under relatively low temperature curing conditions of 160° C. or lower (preferably about 90° C.) because it has an epoxy group and an acid group; and, Since it is a long-chain acid whose acid group is relatively deviated from the main chain, the acid group becomes very easy to react with the epoxy group, and the cross-linking reaction is also carried out at a relatively low temperature, so that a firm hardened film can be formed; if it contains When the side chain of the structural unit of the acid group becomes longer, the glass transition temperature becomes lower than that of the structural unit of acrylic acid or methacrylic acid, the polymer side chain becomes more flexible, and the above-mentioned cross-linking reaction is easily carried out at low temperature.

The copolymer of the present invention has the epoxy group-containing structural unit (A) and the acid group-containing structural unit (B) described above, and has an epoxy equivalent (g/equivalent) of 20,000 or less. When the epoxy equivalent exceeds 20,000, the curing becomes insufficient, and there is a possibility that the solvent resistance is lowered. The epoxy equivalent of the copolymer of the present invention is preferably 10,000 or less, more preferably 8,000 or less, still more preferably 5,000 or less, still more preferably 4,000 or less, particularly preferably 3,000 or less, and most preferably 2,000 or less. In addition, from the viewpoint of storage stability, the epoxy equivalent is preferably 100 or more, more preferably 150 or more, and still more preferably 200 or more. The said epoxy equivalent can be calculated|required by dividing the solid content amount of a copolymer by the molar number of epoxy groups contained in a copolymer. In addition, the said epoxy equivalent can also be calculated|required by the method based on JISK7236:2001.

<Structural Unit (A)> The copolymer of the present invention has an epoxy group-containing structural unit (A) represented by the above-mentioned general formula (1). In the above general formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a direct bond or a divalent organic group. Examples of the above-mentioned organic group include chain or cyclic saturated or unsaturated hydrocarbon groups, -O-, -CO-, -COO-, -NH-, -S-, -SO-, -SO ₂ -, and bivalent bases composed of such combinations. As said hydrocarbon group, a divalent aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group are mentioned. The aliphatic hydrocarbon group may be linear or branched, and examples thereof include a methylene group, an ethylidene group, a trimethylene group, a propylene group, an ethylene group, a propylene group, and an isopropylidene group. Alkyl or vinylidene, propenylene, vinylidene, etc. Examples of the alicyclic hydrocarbon group include cycloalkylene groups such as 1,2-cyclopentylene, 1,2-cyclohexylene, cyclopentylene, and cyclohexylene. Examples of the above-mentioned aromatic hydrocarbon group include 1,2-phenylene, 1,2-naphthylene, 2,3-naphthylene, benzylidene, phenylallylene, biphenylene )Wait.

In the above-mentioned hydrocarbon group, at least one atom constituting the hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom. Moreover, the said hydrocarbon group may have a substituent. As said substituent, a hydroxyl group, an alkoxy group, an alkyl group, an allyl group, an aryl group, a halogen atom, etc. are mentioned. The said substituent may further have a substituent.

Specific examples of the divalent organic group include -R-, -CO-, -CO-R-, -R-CO-R'-, -COO-, -COO-R-, -R -COO-R'-, -O-R-, -R-O-R'- (in the formula, R and R' are the same or different, and represent the above-mentioned divalent hydrocarbon group) and the like.

The number of atoms of the divalent organic group is preferably 0-10, more preferably 1-5, and still more preferably 2-4.

Among them, R ² is preferably -R-, -COO-, -COO-R-, more preferably -COO-, -COO-R- (R represents a hydrocarbon group with 1 to 4 carbon atoms that may have a substituent, preferably It is preferably an alkylene group having 1 to 2 carbon atoms).

X represents an epoxy group-containing group. In this specification, the above-mentioned epoxy group-containing group is a group containing an oxirane ring (epoxy group), a group in which an oxirane ring is bonded to carbon such as glycidyl group, or a group such as epoxy group. The propyl ether group and the glycidyl ester group generally contain an ether bond or an ester bond, and an alicyclic epoxy group containing an epoxycyclohexane ring or the like. As said epoxy group containing group, the group represented by following formula (x1)-(x4) is mentioned, for example.

In the formula, n is an integer of 0-10, preferably an integer of 0-4, more preferably an integer of 0-2. m is an integer of 1-10, Preferably it is an integer of 2-8, More preferably, it is an integer of 3-6. Among them, X is preferably (x1) in terms of reactivity, and more preferably (x1) where n=1.

It is preferable that the said structural unit (A) is a structural unit (A-1) represented by following general formula (1-1) from the point which can further improve solvent resistance.

（式（1-1）中，R ¹表示氫原子或甲基；R ⁶表示直接鍵結或二價有機基）。

(In formula (1-1), R ¹ represents a hydrogen atom or a methyl group; R ⁶ represents a direct bond or a divalent organic group).

In the above general formula (1-1), R ¹ represents a hydrogen atom or a methyl group. Among them, R ¹ is preferably a methyl group. As a divalent organic group represented by R< ⁶ >, the same group as the divalent organic group represented by said R< ² > is mentioned, for example. The carbon number of the divalent organic group represented by R ⁶ is preferably 0-10, more preferably 1-4, still more preferably 1-2.

Among them, the divalent organic group represented by R ⁶ is preferably a divalent aliphatic hydrocarbon group, more preferably a divalent aliphatic hydrocarbon group without a substituent, and more preferably a methylene group.

The copolymer having the above-mentioned structural unit (A) can be obtained by polymerizing a monomer component containing a monomer into which the above-mentioned structural unit (A) can be introduced. As a monomer which can introduce|transduce the said structural unit (A), the compound represented by following formula (a) is mentioned, for example.

（式中，R ¹、R ²及X分別與上述通式（1）中之R ¹、R ²及X相同）。

(In the formula, R ¹ , R ² and X are the same as R ¹ , R ² and X in the above general formula (1), respectively).

Specific examples of the monomer into which the above-mentioned structural unit (A) can be introduced include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, and β (meth)acrylate. -Ethylglycidyl ether, vinylbenzylglycidyl ether, allylglycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, vinyl epoxy ring Hexane etc. Among them, glycidyl (meth)acrylate and (3,4-epoxycyclohexyl)methyl (meth)acrylate are preferred, and glycidyl (meth)acrylate is more preferred, which can suppress side effects. In terms of the reaction and improvement of storage stability, glycidyl methacrylate is more preferred.

The copolymer of the present invention may have one or two or more of the above-mentioned structural units (A).

In the copolymer of the present invention, the content ratio of the structural unit (A) is preferably 0.1 to 50 mass %, more preferably 0.5 mass % or more, and further preferably 1 mass % with respect to 100 mass % of all the structural units. As mentioned above, it is more preferable that it is 45 mass % or less, and it is still more preferable that it is 40 mass % or less.

<Structural unit (B)> The copolymer of the present invention further has an acid group-containing structural unit (B) represented by the above-mentioned general formula (2).

In the above general formula (2), R ³ represents a hydrogen atom or a methyl group. R ⁴ represents a direct bond or an organic group. As the organic group represented by R ⁴ , the same groups as the organic group represented by R ² above may be mentioned. The number of atoms of the organic group represented by R ⁴ is preferably 1-10, more preferably 1-8, still more preferably 2-5. The organic group represented by R ⁴ is preferably a divalent organic group which may have a substituent, preferably a divalent organic group containing an ester bond, more preferably -CO-OR- (R represents a carbon number of 1 to 3 divalent aliphatic hydrocarbon group), -CO-OR(-O-CO-R')-(R represents a linear or branched divalent aliphatic hydrocarbon group with 1 to 3 carbon atoms; R' represents carbon number 1 to 3 monovalent aliphatic hydrocarbon groups), more preferably -CO-OR- (R represents a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms).

R ⁵ represents a bond chain having a length of 2 atoms or more. The length of the above-mentioned bonding chain refers to the number of atoms connected to the main chain of the bonding chain, and does not include the number of atoms constituting the side chain of the bonding chain. Specifically, for example, as a bond chain having a length of 2 atoms, -CH ₂ -CH ₂ -, -C(CH ₃ )-CH ₂ -, -C(CH ₃ )-C(CH ₃ ) can be mentioned. -, -CH ₂ -O-, -O-CH ₂ -, -CO-O-, -CH=CH-, etc.; as a bond chain with a length of 3 atoms, for example: -CH ₂ -CH ₂ - CH ₂ -, -CH ₂ -O-CH ₂ -, -CO-O-CH ₂ -, -CH ₂ -O-CO-, -CH=CH-CH ₂ - and the like. When the length of the bond chain is 0, it has the same meaning as "direct bond".

The length of the bond chain represented by R ⁵ is preferably 10 or less, more preferably 5 or less, and most preferably 2, from the viewpoint of being more excellent in crosslinkability.

The above-mentioned bonding chain is preferably a divalent organic group. As said divalent organic group, the same group as the divalent organic group represented by said R< ² > is mentioned, for example. Among them, the above-mentioned organic groups are preferably -R-, -OR-, -ORO-, -CO-R-, -ORO-CO-R'- (R and R' are the same or different, indicating that they may have two substituents valent hydrocarbon group), more preferably -R-, -OR-, -ORO-CO-R'- (R and R' are the same or different, and represent a divalent aliphatic hydrocarbon group that may have a substituent), and more preferably an extension ethyl.

Y represents an acid group. Examples of the acid group include functional groups that undergo a neutralization reaction with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group. 2 or more. Among them, a carboxyl group or a carboxylic acid anhydride group is preferable, and a carboxyl group is more preferable. Moreover, it may have two or more acid groups.

a represents 0 or 1. From the viewpoint of more excellent solvent resistance, a is preferably 1.

As said structural unit (B), the structural unit (B-1) represented by following general formula (2-1) is mentioned preferably.

（式（2-1）中，R ³表示氫原子或甲基；R ⁷及R ⁸相同或不同，表示直接鍵結或有機基；b表示0或1）。

(In formula (2-1), R ³ represents a hydrogen atom or a methyl group; R ⁷ and R ⁸ are the same or different, and represent a direct bond or an organic group; b represents 0 or 1).

In the above general formula (2-1), R ³ represents a hydrogen atom or a methyl group. R ³ is preferably a methyl group in that the heat resistance or developability of the polymer becomes favorable. Preferred examples of the organic group represented by R ⁷ and R ⁸ include the above-mentioned divalent organic groups and the like. Among them, R ⁷ is preferably a divalent hydrocarbon group which may have a substituent, and more preferably a second which may have a substituent. A valence aliphatic hydrocarbon group, more preferably an alkylene group. As R ⁸ , a divalent hydrocarbon group which may have a substituent is preferable, a divalent aliphatic hydrocarbon group which may have a substituent is more preferable, and an alkylene group is still more preferable.

The number of carbon atoms in the organic group represented by R ⁷ and R ⁸ is preferably 1-10, more preferably 1-5, and still more preferably 1-3.

b represents 0 or 1, but 1 is preferable in that the solvent resistance can be further improved.

The copolymer having the above-mentioned structural unit (B) can be obtained by polymerizing an acid group-containing compound with "a base polymer obtained by polymerizing a monomer component containing a monomer into which the above-mentioned structural unit (B) can be introduced" or A base polymer obtained by polymerizing a monomer component containing a hydroxyl group-containing monomer is obtained by reacting.

Examples of monomers into which the structural unit (B) can be introduced include β-carboxyethyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, and mono(2-methyl succinate) Long-chain unsaturated monocarboxylic acids formed by chain extension between unsaturated groups such as acryloxyethyl) esters and carboxyl groups, etc.

As said hydroxyl-containing monomer, the compound represented by following formula (b1) is mentioned, for example.

（式中，R ³及R ⁴分別與上述通式（2）中之R ³及R ⁴相同）。

(In the formula, R ³ and R ⁴ are the same as R ³ and R ⁴ in the above-mentioned general formula (2), respectively).

Specific examples of the above-mentioned hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylate ) Hydroxyalkane (meth)acrylate such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, etc. base ester; glycerol mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, neotaerythritol mono(meth)acrylate, di-trimethylolpropane mono(meth)acrylate Mono(meth)acrylates of polyols such as acrylates and dipivalerythritol mono(meth)acrylates; hydroxyalkyl acrylamides such as N-hydroxyethyl acrylamide.

As said acid group containing compound, the compound represented by following formula (b2) or formula (b3) is mentioned, for example.

（式中，R ⁵及Y分別與上述通式（2）中之R ⁵及Y相同）。

(In the formula, R ⁵ and Y are the same as R ⁵ and Y in the above-mentioned general formula (2), respectively).

（式中，R ⁵與上述通式（2）中之R ⁵相同）。

(In the formula, R ⁵ is the same as R ⁵ in the above general formula (2)).

Specific examples of the acid group-containing compound include carboxylic acids such as succinic acid, maleic acid, phthalic acid, tetrahydrophthalic acid, and trimesic acid; succinic anhydride , maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, 1,2,4-benzene Carboxylic acid anhydrides such as tricarboxylic acid anhydride and the like. Among them, carboxylic anhydrides are preferred, and succinic anhydrides are more preferred in terms of higher addition reactivity.

The specific method for obtaining the copolymer which has the said structural unit (B) is demonstrated in detail in the manufacturing method of the following polymer.

The copolymer of the present invention may have one kind or two or more kinds of structural units (B).

In the copolymer of the present invention, the content ratio of the structural unit (B) is preferably 0.1 to 50% by mass, more preferably 0.2% by mass or more, and more preferably 1% by mass relative to 100% by mass of all the structural units As mentioned above, it is more preferable that it is 45 mass % or less, and it is still more preferable that it is 40 mass % or less.

<Structural unit (C)> The copolymer of the present invention is preferably a copolymer further having a ring structure in the main chain. That is, it is preferable that the said copolymer further has the structural unit (C) which has a ring structure in a main chain. If the said copolymer is a polymer which has a ring structure in a main chain, the hardened|cured material excellent also in heat resistance can be formed. As said ring structure, an imide ring, a tetrahydropyran ring, a tetrahydrofuran ring, a lactone ring, etc. are mentioned. A copolymer having the above-mentioned structural unit (C) can be obtained by polymerizing a monomer component containing a monomer capable of introducing a ring structure to the main chain.

Examples of the above-mentioned monomer capable of introducing a ring structure into the main chain include: a monomer having a ring structure containing a double bond in the molecule; or a monomer that undergoes cyclization polymerization to form a polymer having a ring structure in the main chain; A monomer that forms a ring structure after polymerization. From the viewpoints of good heat resistance, hardness, colorant dispersibility, etc., specifically, preferably selected from N-substituted maleimide-based monomers, 2,2'-(oxydimethylene) at least one monomer in the group consisting of dialkyl diacrylate-based monomers and α-(unsaturated alkoxyalkyl) acrylate-based monomers. Among them, an N-substituted maleimide-based monomer is preferable from the viewpoint of being more excellent in solvent resistance.

Examples of the N-substituted maleimide-based monomers include N-cyclohexylmaleimide, N-phenylmaleimide, and N-methylmaleimide. Diimide, N-ethylmaleimide, N-isopropylmaleimide, N-tert-butylmaleimide, N-dodecylcis-butylene N-benzylmaleimide, N-benzylmaleimide, N-naphthylmaleimide, and the like; one or more of these can be used. Among them, from the viewpoint of heat resistance, preferred are N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, and more Preferred is N-benzylmaleimide.

As said N-benzylmaleimide, for example, benzylmaleimide; p-methylbenzylmaleimide, p-butylbenzylmaleimide, Alkyl-substituted benzylmaleimide such as imide; benzylmaleimide substituted with phenolic hydroxyl such as p-hydroxybenzylmaleimide; orthobenzyl chloride Benzylmaleimide, o-dichlorobenzylmaleimide, p-dichlorobenzylmaleimide, etc. halogen-substituted benzylmaleimide, etc.

As said 2,2'- (oxydimethylene) dialkyl diacrylate type monomer, 2,2'- [oxybis (methylene)]bis-2- acrylate dimethyl ester is mentioned, for example: , 2,2'-[Oxybis(methylene)]bis-2-diethyl acrylate, 2,2'-[Oxybis(methylene)]bis-2-acrylate di(n-propyl)ester , 2,2'-[Oxybis(methylene)]bis-2-acrylic acid di(isopropyl) ester, 2,2'-[oxybis(methylene)]bis-2-acrylic acid di(n-propyl) butyl) ester, 2,2'-[oxybis(methylene)]bis-2-acrylate di(isobutyl), 2,2'-[oxybis(methylene)]bis-2- Di(tert-butyl) acrylate, 2,2'-[oxybis(methylene)]bis-2-acrylate, bis(tert-pentyl)acrylate, 2,2'-[oxybis(methylene) )] bis-2-acrylate bis(stearyl) ester, 2,2'-[oxybis(methylene)]bis-2-acrylate bis(lauryl) ester, 2,2'-[oxybis(methylene)] methylene)]bis-2-acrylate bis(2-ethylhexyl)ester and the like. Among these, dimethyl 2,2'-[oxybis(methylene)]bis-2-acrylate is more preferable from the viewpoints of transparency, dispersibility, industrial availability, and the like.

As said alpha-(unsaturated alkoxyalkyl) acrylate type monomer, an alpha-(allyloxymethyl) acrylate type monomer is mentioned, for example. Specific examples of the above-mentioned α-(allyloxymethyl) acrylate monomers include α-allyloxy methacrylic acid; α-allyloxy methyl methacrylate; α-ene Propoxy ethyl methacrylate, α-allyloxy methacrylate n-propyl, α-allyloxy methacrylate isopropyl, α-allyloxy methacrylate n-butyl, α- Second butyl allyloxy methacrylate, third butyl α-allyloxy methacrylate, n-pentyl α-allyloxy methacrylate, second α-allyloxy methacrylate Amyl ester, 3-amyl α-allyloxy methacrylate, n-hexyl α-allyloxy methacrylate, 2-hexyl α-allyloxy methacrylate, α-allyloxy methyl acrylate n-heptyl acrylate, n-octyl α-allyloxy methacrylate, 2 octyl α-allyloxy methacrylate, 3 octyl α-allyloxy methacrylate, α-ene 2-Ethylhexyl Propoxymethacrylate, Octyl α-allyloxy methacrylate, Nonyl α-allyloxy methacrylate, Decyl α-allyloxy methacrylate, α-allyloxy methacrylate -Undecyl allyloxymethacrylate, lauryl alpha-allyloxymethacrylate, tridecyl alpha-allyloxymethacrylate, alpha-allyloxymethacrylic acid Myristyl, α-allyloxypentadecyl methacrylate, α-allyloxy hexadecyl methacrylate, α-allyloxy heptadecyl methacrylate, α-allyloxy methacrylate - octadecyl allyloxymethacrylate, nonadecyl α-allyloxymethacrylate, eicosyl α-allyloxymethacrylate, α-allyloxy (α-allyloxymethyl) acrylic acid alkyl ester monomers such as methacrylic acid wax ester, α-allyloxy methacrylic acid beeswax ester; α-allyloxy methacrylate methoxyethyl ester Esters, α-allyloxymethacrylate methoxyethoxyethyl, α-allyloxymethacrylate methoxyethoxyethoxyethyl, α-allyloxymethacrylic acid 3-Methoxybutyl ester, α-allyloxymethacrylate ethoxyethyl, α-allyloxymethacrylate ethoxyethoxyethyl, α-allyloxymethacrylic acid (α-allyloxymethyl) alkoxyalkyl acrylate monomers such as phenoxyethyl ester, α-allyloxy methacrylate phenoxyethoxyethyl ester; α-allyloxy Hydroxyethyl methacrylate, α-allyloxy hydroxypropyl methacrylate, α-allyloxy hydroxybutyl methacrylate, α-allyloxy fluoroethyl methacrylate, α-ene Difluoroethyl Propoxymethacrylate, Chloroethyl α-allyloxymethacrylate, Dichloroethyl α-allyloxymethacrylate, Bromoethyl α-allyloxymethacrylate , α-allyloxy dibromoethyl methacrylate, α-allyloxy vinyl methacrylate, α-allyloxy allyl methacrylate, α-allyloxy methyl methacrylate Alkyl allyl ester, α-allyloxy crotyl methacrylate, α-allyloxy propynyl methacrylate, α-allyloxy cyclopentyl methacrylate, α-allyloxy methyl acrylate Cyclohexyl acrylate, α-allyloxymethacrylic acid 4-Methylcyclohexyl, α-allyloxymethacrylate 4-tert-butylcyclohexyl, α-allyloxymethacrylate tricyclodecyl, α-allyloxymethacrylic acid Isobornate, α-allyloxy methacrylate adamantyl, α-allyloxy methacrylate dicyclopentadienyl, α-allyloxy phenyl methacrylate, α-allyloxy Methyl phenyl methacrylate, α-allyloxy dimethyl phenyl methacrylate, α-allyloxy methacrylate trimethyl phenyl, α-allyloxy methacrylate 4-th Tributylphenyl ester, α-allyloxybenzyl methacrylate, α-allyloxydiphenylmethyl methacrylate, α-allyloxydiphenylethyl methacrylate, α- Triphenylmethyl allyloxymethacrylate, phenylallyl α-allyloxymethacrylate, naphthyl α-allyloxymethacrylate, anthracene α-allyloxymethacrylate Wait. Among them, (α-allyloxymeth)acrylate-based monomers are preferred. As the above-mentioned (α-allyloxymeth)acrylate-based monomer, α-allyloxymethacrylic acid is particularly preferred from the viewpoints of transparency, dispersibility, industrial availability, and the like Methyl ester (also known as (alpha-allyloxymethyl)acrylate methyl ester).

The above-mentioned α-(unsaturated alkoxyalkyl)acrylate can be produced, for example, by the production method disclosed in the pamphlet of International Publication No. 2010/114077.

As a monomer which can introduce|transduce a ring structure into a main chain, 2-(hydroxyalkyl) acrylic acid alkyl ester is mentioned preferably. Alkyl 2-(hydroxyalkyl)acrylate can react with (meth)acrylic acid to form a lactone ring structure in the main chain.

Examples of the above-mentioned 2-(hydroxyalkyl)acrylic acid alkyl ester include 2-(1-hydroxyalkyl)acrylic acid alkyl ester and 2-(2-hydroxyalkyl)acrylic acid alkyl ester; specifically, for example Examples include: methyl 2-(1-hydroxymethyl)acrylate, ethyl 2-(1-hydroxymethyl)acrylate, isopropyl 2-(1-hydroxymethyl)acrylate, 2-(1-methylol)acrylate base) n-butyl acrylate, 3-butyl 2-(1-hydroxymethyl) acrylate, 2-ethylhexyl 2-(1-hydroxymethyl) acrylate, and the like. Among them, methyl 2-(1-hydroxymethyl)acrylate and ethyl 2-(1-hydroxymethyl)acrylate are preferred. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The said copolymer may have 1 type or 2 or more types of structural unit (C).

In the above-mentioned copolymer, the content ratio of the above-mentioned structural unit (C) is preferably 0.1 to 50% by mass, more preferably 0.2% by mass or more, more preferably 1% by mass or more, relative to 100% by mass of all the structural units, Moreover, it is more preferable that it is 45 mass % or less, and it is still more preferable that it is 40 mass % or less.

<Structural unit (D)> The said copolymer may further have another structural unit (D) in addition to the said structural unit (A), (B), and (C). As said structural unit (D), in addition to the structural unit derived from the above-mentioned hydroxyl-containing monomer, for example, an acid group-containing monomer other than the above-mentioned long-chain unsaturated monocarboxylic acid, (methyl ) Structural units of acrylate-based monomers, monomers having groups that generate acid groups, and other copolymerizable monomers.

Examples of the acid group-containing monomer include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and vinyl benzoic acid; maleic acid, fumaric acid, Unsaturated polycarboxylic acids such as Aconic acid, citraconic acid, and mesaconic acid; Unsaturated acid anhydrides such as maleic anhydride and Iconic anhydride; Saturated compounds, etc.

啉、4-(甲基)丙烯醯氧基甲基-2-甲基-2-乙基-1,3-二氧環戊烷（4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane）、4-(甲基)丙烯醯氧基甲基-2-甲基-2-異丁基-1,3-二氧環戊烷、4-(甲基)丙烯醯氧基甲基-2-甲基-2-環己基-1,3-二氧環戊烷、4-(甲基)丙烯醯氧基甲基-2,2-二甲基-1,3-二氧環戊烷等。As said (meth)acrylate type monomer, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, (meth)acrylate 2-ethylhexyl acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylic acid Lauryl ester, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (meth)acrylic acid (3,4) - Epoxycyclohexyl) methyl ester, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate , 2-ethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-di(meth)acrylate Ethylaminoethyl ester, 1,4-dioxaspiro[4,5]dec-2-ylmethacrylic acid, (meth)acryloyl

phenoline, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane (4-(meth)acryloyloxymethyl-2-methyl-2-ethyl- 1,3-dioxolane), 4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxy Alkylmethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-di Oxycyclopentane etc.

As a monomer which has the group which produces|generates the said acid group, the compound which has a group which produces|generates an acid group by heat or an acid, and a polymerizable double bond is mentioned. As said polymerizable double bond, a (meth)acryloyl group, a vinyl group, an allyl group, a methallyl group etc. are mentioned, for example. Examples of the above-mentioned groups that generate acid groups by heat or acid include tertiary carbon-containing groups, groups obtained by capping acid groups with vinyl ether compounds, groups formed by tertiary butyl groups or acetyl groups A protecting group such as a phenolic hydroxyl group protects a phenolic hydroxyl group, etc.

Preferred examples of the tertiary carbon-containing group include groups represented by -COO ^* R ^a (R ^a represents a monovalent organic group, and the carbon atom bonded to O ^* is a tertiary carbon atom) group. The OC bond between -COO ^* and ^Ra is cleaved by heating to generate a carboxyl group.

The above-mentioned R ^a of -COO ^* R ^a represents a monovalent organic group, and the carbon atom bonded to O ^* is a tertiary carbon atom. A tertiary carbon atom means a carbon atom having three other carbon atoms bonded to the carbon atom.

As the above-mentioned monovalent organic group, preferably, a monovalent chain, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 91 carbon atoms is mentioned. The above-mentioned organic group may have a substituent. The carbon number of R ^a is more preferably carbon number 1-50, more preferably carbon number 1-35, more preferably carbon number 1-20, particularly preferably carbon number 1-12, most preferably carbon number 1- 9.

R ^a may be preferably represented by -C(R ^b )(R ^c )(R ^d ). In this case, R ^b , R ^c and R ^d are the same or different, preferably a hydrocarbon group having 1 to 30 carbon atoms. The above-mentioned hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, may have a cyclic structure, or may have a substituent. In addition, R ^b , R ^c and R ^d may be linked to each other at the terminal portion to form a cyclic structure.

Here, in the above-mentioned tertiary carbon-containing group, the tertiary carbon atom is preferably at least one of adjacent carbon atoms bonded to a hydrogen atom. For example, when R ^a is a group represented by -C(R ^b )(R ^c )(R ^d ), preferably at least one of R ^b , R ^c and R ^d includes at least one A carbon atom of a hydrogen atom, and the carbon atom is bonded to a tertiary carbon atom. The above R ^b , R ^c and R ^d are the same or different, preferably a saturated hydrocarbon group with 1 to 15 carbon atoms, more preferably a saturated hydrocarbon group with 1 to 10 carbon atoms, and more preferably a saturated hydrocarbon group with 1 to 5 carbon atoms, Particularly preferred is a saturated hydrocarbon group having 1 to 3 carbon atoms. The above R ^a is preferably a tertiary butyl group or a tertiary pentyl group.

Preferable examples of the tertiary carbon-containing monomer include tertiary butyl (meth)acrylate, tertiary amyl (meth)acrylate, and the like.

As a group formed by capping an acid group with the above-mentioned vinyl ether compound, a group formed by bonding a vinyl ether compound to the above-mentioned acid group such as a carboxyl group is exemplified. Examples of the vinyl ether compound include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and tert-butyl vinyl ether. , 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether and other aliphatic vinyl ether compounds; or dihydropyran and other cyclic ether compounds that can be ring-opened to produce vinyl ether, etc. Among the above-mentioned vinyl ether compounds, dihydropyran is preferred in that the protecting group is easily detached at a lower temperature.

As a group formed by capping an acid group with the above-mentioned dihydropyran, a group represented by the following formula is preferably used.

As a group which protects a phenolic hydroxyl group by the protecting group, such as the said t-butyl group or an acetyl group, the group represented by the following formula is mentioned preferably.

（式中，n表示取代基之數量，且為1～5之整數）。

(In the formula, n represents the number of substituents, and is an integer of 1 to 5).

The group represented by the above formula is, for example, reacted in a solvent under an acid catalyst such as hydrochloric acid and sulfuric acid at a temperature of 50 to 150° C. for 1 to 30 hours to remove the protective group, thereby generating an acid group.

Specific examples of the monomer having a group represented by the above formula include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenyl phenol, m-isopropenyl phenol, o-isopropene Monomers in which the hydroxyl groups of aromatic vinyl compounds having phenolic hydroxyl groups are protected by tertiary butyl and acetyl groups.

Among them, in terms of generating an acid group at a lower temperature, as a monomer having a group generating the above-mentioned acid group, a monomer having a group formed by capping the acid group with the above-mentioned dihydropyran is preferable monomer.

啉、N-乙烯基乙醯胺等N-乙烯系化合物類；(甲基)丙烯酸異氰酸基乙酯、異氰酸烯丙基酯等不飽和異氰酸酯類等。 Examples of the above-mentioned other copolymerizable monomers include one or more of the following compounds and the like. Examples include: (meth)acrylamides such as N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, and N-isopropylacrylamide; polyacrylamides; Styrene, poly(meth)acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactone are equal to one end of the polymer molecular chain with (methyl) ) Acryloyl giant monomers; 1,3-butadiene, isoprene, chloroprene and other conjugated dienes; vinyl acetate, vinyl propionate, vinyl butyrate, benzoic acid Vinyl esters such as vinyl esters; aromatic vinyls such as styrene, vinyltoluene, α-methylstyrene, xylene, methoxystyrene, ethoxystyrene; methyl vinyl ether, ethyl vinyl ether , propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether , methoxyethoxyethyl vinyl ether, methoxy polyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and other vinyl ethers; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinyl

N-vinyl compounds such as linoline and N-vinylacetamide; unsaturated isocyanates such as isocyanatoethyl (meth)acrylate and allyl isocyanate, etc.

Among them, as a monomer that provides the above-mentioned structural unit (D), for example, by copolymerizing a monomer having an amide group such as the above-mentioned (meth)acrylamides, an addition reaction can be performed without using an alkaline catalyst such as an amine, And can improve the storage stability of the copolymer. In addition, in the case of using a monomer having an amine group such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate, it is not necessary to use a contact The addition reaction of the medium can be carried out, and the storage stability of the copolymer can be improved.

In addition, as the monomer that provides the above-mentioned structural unit (D), it is preferable to use a monomer with a long side chain or a monomer with a large steric hindrance from the viewpoint that the gelation is suppressed and the storage stability becomes good. body. As the monomer having a long side chain, the number of atoms in the longest side chain of the monomer is preferably 5 to 20, more preferably 6 to 20, and still more preferably 7 to 10. The above-mentioned side chain may be linear or branched. As a specific example of the monomer with the said long side chain, 2-ethylhexyl (meth)acrylate is mentioned preferably.

As the above-mentioned monomer with large steric hindrance, those having a ring structure in the side chain are preferably mentioned, for example, those having a cyclohexyl group, a bicyclic ring, a phenyl group, a biphenyl group, a dicyclopentyl group, a furan, a piperane, and a piperidine are mentioned. and other structures. Specific examples of the aforementioned monomers with large steric hindrance include vinyltoluene, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylate ) 1-adamantyl acrylate, (meth)acrylate (meth)acrylate phenoxyethyl, (meth)acrylic acid, (meth)acrylate dicyclopentyl, (meth)acrylate dicyclopentenyl , (meth) tricyclodecyl acrylate, (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylate pentamethyl piperidine, etc. Among them, dicyclopentyl (meth)acrylate, vinyltoluene, benzyl (meth)acrylate, and cyclohexyl (meth)acrylate are preferred.

Among them, the above-mentioned copolymer preferably has a compound derived from the group consisting of vinyltoluene, 2-ethylhexyl (meth)acrylate, and dicyclopentane (meth)acrylate from the viewpoint that the storage stability can be further improved. The structural unit of at least one monomer in the group of esters. Moreover, when the said copolymer has the structural unit derived from 2-ethylhexyl (meth)acrylate, the glass transition temperature of a copolymer will fall and developability can be improved.

The said copolymer may have 1 type or 2 or more types of structural unit (D).

In the above-mentioned copolymer, the content ratio of the above-mentioned structural unit (D) is preferably 0.1 to 50% by mass, more preferably 0.2% by mass or more, more preferably 1% by mass or more, relative to 100% by mass of all the structural units, Moreover, it is more preferable that it is 45 mass % or less, and it is still more preferable that it is 40 mass % or less.

The acid value of the above-mentioned copolymer is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, and still more preferably 30 mgKOH/g or more. Moreover, 300 mgKOH/g or less is preferable, 250 mgKOH/g or less is more preferable, 200 mgKOH/g or less is still more preferable, and 100 mgKOH/g or less is still more preferable. The above acid value is a value measured by neutralization titration using a potassium hydroxide (KOH) solution, and is an acid value per 1 g of polymer solid content.

The weight average molecular weight of the above-mentioned copolymer is preferably 2,000 or more, more preferably 3,000 or more, and still more preferably 4,000 or more. Moreover, it is preferably 250,000 or less, more preferably 100,000 or less, still more preferably 50,000 or less, and still more preferably 20,000 or less. The weight average molecular weight of the above-mentioned copolymer can be measured by gel permeation chromatography (GPC) method, and specifically, can be measured by the method described in the examples.

The above-mentioned copolymer may have a polymerizable double bond (carbon-carbon double bond) in the side chain. Since the side chain has a polymerizable double bond, the photohardenability of the copolymer can be improved. As said polymerizable double bond, the above-mentioned ones are mentioned, Among them, a (meth)acryloyl group is preferable.

When the copolymer has a polymerizable double bond in the side chain, the double bond equivalent of the copolymer is preferably 200 to 20000 g/equivalent. In terms of improving the hardenability, the double bond equivalent is more preferably 250 to 15000 g/equivalent, more preferably 300 to 10000 g/equivalent, still more preferably 300 to 4000 g/equivalent.

The above-mentioned double bond equivalent is the mass of the solid content of the polymer solution per 1 mol of the double bond of the above-mentioned copolymer. The mass of the solid content of the polymer solution is obtained by adding up the mass of the monomers constituting the copolymer and the mass of the polymerization inhibitor. The said double bond equivalent can be calculated|required by dividing the mass (g) of the polymer solid content of a polymer solution by the double bond amount (mol) of a copolymer. The double bond amount of the said copolymer can be calculated|required based on the quantity of the monomer containing an acid group and the compound which has a polymerizable double bond used at the time of superposition|polymerization. Moreover, it can also measure using various analyses, such as titration, elemental analysis, NMR, and IR, or a differential scanning calorimeter method. For example, it can also be calculated by measuring the number of ethylenic double bonds contained in 1 g of the copolymer in accordance with the test method of the iodine value described in JIS K 0070:1992.

<Production method of copolymer> The method for producing the copolymer of the present invention is not particularly limited as long as it is a method for obtaining a copolymer having at least the above-mentioned structural unit (A) and structural unit (B) and having an epoxy equivalent in a specific range. Examples include: a method of polymerizing a monomer component containing a monomer that can be introduced into each of the above-mentioned structural units; or polymerizing the monomer component to obtain a base polymer, and adding other compounds to the groups possessed by the above-mentioned base polymer. A method for obtaining a polymer with a specific structural unit through a reaction, etc.

The method of polymerizing the above-mentioned monomer components is not particularly limited, and commonly used methods such as block polymerization, solution polymerization, and emulsion polymerization can be used. Among them, solution polymerization is preferred because it is industrially advantageous and the structure such as molecular weight can be easily adjusted. In addition, the polymerization mechanism of the above-mentioned monomer components may use a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, etc., but in terms of industrial advantages, it is preferably based on a radical polymerization mechanism. Aggregation method. In addition, the molecular weight of the polymer obtained by polymerizing the above-mentioned monomer components can be controlled by appropriately adjusting the amount or kind of the polymerization initiator, the polymerization temperature, and the kind or amount of the chain transfer agent.

As the above-mentioned polymerization initiator, peroxides, azo compounds, etc., which are generally used as polymerization initiators, can be exemplified. As said chain transfer agent, the compound etc. which have a mercapto group, such as alkylthiols, mercaptocarboxylic acids, and mercaptocarboxylic acid esters, which are generally used as a chain transfer agent, are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, these addition amounts can be suitably set according to a well-known method.

烷、乙二醇二甲醚、二乙二醇二甲醚等醚類；丙酮、甲基乙基酮等酮類；乙酸乙酯、乙酸丁酯、丙二醇單甲醚乙酸酯、乙酸3-甲氧基丁酯等酯類；甲苯、二甲苯、乙基苯等芳香族烴類；氯仿；二甲基亞碸；碳酸二甲酯等。該等溶劑可單獨使用或將2種以上組合使用。As the solvent used for the above-mentioned polymerization, for example, tetrahydrofuran, dihydrofuran,

alkane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and other ethers; acetone, methyl ethyl ketone and other ketones; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, acetic acid 3- Esters such as methoxybutyl ester; Aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform; dimethyl sulfoxide; dimethyl carbonate, etc. These solvents may be used alone or in combination of two or more.

The polymerization concentration at the time of polymerizing the monomer composition (reaction liquid) containing the above-mentioned monomer components is preferably 5 to 90 mass %, more preferably 5 to 70 mass %, still more preferably 10 to 60 mass %. The above-mentioned polymerization concentration refers to the mass % of the monomer used relative to 100 mass % of the reaction solution.

Regarding the above polymerization conditions, the polymerization temperature may be appropriately set according to the type and amount of the monomer used, the type and amount of the polymerization initiator, and the like, for example, preferably 50 to 130° C., more preferably 60 to 120° C. °C. Moreover, the polymerization time can also be suitably set similarly, for example, 1 to 5 hours are preferable, and 2 to 4 hours are more preferable.

As a method for producing the above-mentioned copolymer, for example, a method including the step of adding an epoxy group-containing monomer represented by the above formula (a) and a hydroxyl group-containing monomer represented by the above formula (b1) can be mentioned. The step (1) of polymerizing the monomer components of the polymer; and the step of reacting the polymer obtained in the above-mentioned polymerization step (1) with the acid group-containing compound represented by the above-mentioned formula (b2) or formula (b3) ( 2). By producing the above-mentioned copolymer by such a method, gelation at the time of producing the copolymer can be suppressed, and a copolymer having the above-mentioned structural unit (A) and structural unit (B) can be obtained efficiently. That is, the present invention is also a method for producing a copolymer, characterized by comprising: mixing a monomer comprising an epoxy group-containing monomer represented by formula (a) and a hydroxyl group-containing monomer represented by formula (b1). The step (1) of polymerizing the body component; and the step (2) of reacting the polymer obtained in the above-mentioned polymerization step (1) with the acid group-containing compound represented by the above-mentioned formula (b2) or formula (b3).

Each step in the above-mentioned production method will be described. step 1) In the manufacturing method of the copolymer of this invention, the monomer component containing the epoxy group containing monomer represented by said formula (a) and the hydroxyl group containing monomer represented by said formula (b1) is polymerized. As an epoxy group-containing monomer represented by the said formula (a), the monomer etc. which were described as the monomer which can introduce|transduce the structural unit (A) of the said copolymer are mentioned, for example. As the above-mentioned hydroxyl group-containing monomer represented by the above-mentioned formula (b1), the above-mentioned ones can be mentioned.

The content ratio of the epoxy group-containing monomer and the hydroxyl group-containing monomer is not particularly limited, as long as the content ratio of the structural unit (A) and the structural unit (B) in the obtained copolymer is equal to the content ratio of the structural unit (A) and the structural unit (B). The method can be set appropriately.

The above-mentioned monomer components may also contain other monomer components other than the acid group-containing compound used in the following step (2). As said other monomer component, the said monomer component is mentioned.

The method of polymerizing the above-mentioned monomer components is not particularly limited, and the polymerization may be carried out by the above-mentioned known methods. The polymerization temperature or time is also as described above.

In addition, generally used polymerization initiators, chain transfer agents, catalysts, solvents, etc. may be used for the above-mentioned polymerization.

Step (2) Next, the step of reacting the polymer obtained in the above step (1) with the acid group-containing compound represented by the above formula (b2) or formula (b3) is included. The acid group-containing compound can be added by reacting the polymer (base polymer) obtained in the above step (1) with the acid group-containing compound represented by the above formula (b2) or formula (b3). The hydroxyl groups of the polymer (base polymer) obtained in step (1) form long-chain acid groups.

It does not specifically limit as a reaction method, It can carry out by a well-known method. As reaction temperature, 25-100 degreeC is preferable, for example, More preferably, it is 30-90 degreeC. Although it does not specifically limit as reaction time, For example, 1 to 20 hours are mentioned.

In addition, the step of reacting the above-mentioned acid group-containing compound may be carried out in the presence of a basic compound. By carrying out the reaction in the presence of a basic compound, the reaction of a hydroxyl group and an acid group can be carried out at a lower temperature such as 70°C or lower. Moreover, since the reaction is carried out under the above-mentioned low temperature conditions, the reaction between the epoxy group and the acid group can be suppressed and only the reaction between the hydroxyl group and the acid group can be carried out, so that the above-mentioned structural unit (A) and the structure can be produced more efficiently. A copolymer of unit (B).

For example, in step (2), the polymer (base polymer) obtained in step (1) can also be reacted with the above-mentioned acid group-containing compound at 70°C or lower in the presence of a basic compound. In this case, when it exceeds 70 degreeC, the reaction of an epoxy group and an acid group will progress easily, and there exists a possibility of resin gelation.

啉、N-乙基哌啶、N-乙基

啉、吡啶等雜環狀胺；苄基胺、N-甲基苯胺、N,N-二甲基苯胺等芳香族胺；氯化四甲基銨、氯化四乙基銨等氯化四烷基銨；乙酸四甲基銨等四烷基銨有機酸鹽；硫酸氫四甲基銨、硫酸氫四乙基銨等四烷基銨無機酸鹽；氫氧化四甲基銨、氫氧化四乙基銨、氫氧化單羥基乙基三甲基銨等氫氧化(羥基)烷基銨；鈉、鉀等鹼金屬之氫氧化物；鋇、鍶、鈣、鑭等過渡金屬之氫氧化物；[Pt(NH ₃) ₆](OH) ₄等錯鹽之游離鹽；三苯基膦、三環己基膦、三甲基膦等磷化合物等。其中，就蒸散容易性、操作容易性之方面而言，較佳為二級胺、三級胺、雜環狀胺、磷化合物，就可抑制副反應且抑制加成後之聚合物之分子量上升之方面而言，更佳為三級胺、三苯基膦。 Examples of the acid group-containing compound represented by the above formula (b2) or formula (b3) include the above-mentioned acid group-containing compounds. Examples of the basic compound include ammonia; primary amines such as methylamine; secondary amines such as dimethylamine; tertiary amines such as triethylamine and diethylmethylamine; aliphatic amines such as base amine and diethylamine; cyclic aliphatic amines such as cyclohexylamine; piperidine,

Linen, N-ethylpiperidine, N-ethyl

Heterocyclic amines such as linoline and pyridine; aromatic amines such as benzylamine, N-methylaniline, N,N-dimethylaniline, etc.; tetraalkane chlorides such as tetramethylammonium chloride and tetraethylammonium chloride ammonium; tetraalkylammonium organic acid salts such as tetramethylammonium acetate; tetraalkylammonium inorganic acid salts such as tetramethylammonium hydrogen sulfate, tetraethylammonium hydrogen sulfate; tetramethylammonium hydroxide, tetraethylammonium hydroxide (Hydroxy) alkyl ammonium hydroxides such as ammonium hydroxide, monohydroxyethyl trimethyl ammonium hydroxide; hydroxides of alkali metals such as sodium and potassium; hydroxides of transition metals such as barium, strontium, calcium, and lanthanum;[ Free salts of zirconium salts such as Pt( _NH3 ) ₆ ](OH) ₄ ; phosphorus compounds such as triphenylphosphine, tricyclohexylphosphine, trimethylphosphine, etc. Among them, secondary amines, tertiary amines, heterocyclic amines, and phosphorus compounds are preferred in terms of ease of evaporation and handling, since side reactions can be suppressed and the increase in the molecular weight of the polymer after addition can be suppressed. On the other hand, tertiary amine and triphenylphosphine are more preferable.

The usage amount of the above-mentioned basic compound is not particularly limited. From the viewpoint of reaction efficiency, it is preferably 0-5 mol % relative to the usage amount of the acid group-containing compound 100 mol %, more preferably 0 mol %. ~4 mol %, more preferably 0 to 3 mol %.

The usage-amount of the above-mentioned acid group-containing compound can be appropriately set according to the purpose and application of the copolymer to be obtained, so that the content ratio of the above-mentioned structural unit (B) becomes a desired range or the acid value of the above-mentioned copolymer becomes a desired range. .

The total monomer component concentration of the acid group-containing compound in the total amount of the polymerization solution during the addition reaction is preferably 40% by mass or more, more preferably 50% by mass or more. If the total monomer component concentration is within the above range, the above-mentioned acid group-containing compound can be added to the above-mentioned base polymer without using the above-mentioned basic compound as a catalyst, and the storage stability of the obtained copolymer can be improved. . In this way, if the monomer concentration relative to the total amount of the polymerization solution of the copolymer is high, the acid group-containing compound can be added in the absence of a catalyst, thereby improving the storage stability of the copolymer.

In the above reaction, commonly used catalysts, solvents, and the like can also be used.

In addition, when producing a copolymer having a polymerizable double bond in the side chain, an acid group-containing monomer or an isocyanate group-containing polymerizable monomer can be subjected to addition reaction with a hydroxyl group after the above step (1), or in After the above step (1) or (2), an acid group-containing monomer is subjected to an addition reaction with an epoxy group, whereby a polymerizable double bond is introduced into the side chain of the copolymer. As said acid group-containing monomer, the above-mentioned ones are mentioned, Preferably, (meth)acrylic acid is mentioned. Examples of the above-mentioned isocyanate group-containing polymerizable monomer include the above-mentioned unsaturated isocyanates and the like, and the addition reaction can be performed at low temperature and the storage stability of the copolymer can be improved. Isocyanatoethyl (meth)acrylate is cited. The above-mentioned addition reaction is not particularly limited, and can be carried out by a known method. Moreover, in the said addition reaction, the compound, catalyst, solvent, etc. which are generally used can also be used.

Among them, as the catalyst, the above-mentioned basic compounds are preferably used, and secondary amines, tertiary amines, heterocyclic amines, and phosphorus compounds are preferred, and tertiary amines and triphenylphosphine are more preferred. In addition, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, and dibutyltin dimaleate, which are generally used as catalysts for the reaction of isocyanate monomers and hydroxyl groups, can also be preferably used. , Dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin sulfonate, tributyltin acetate, dioctyltin oxide, tributyltin chloride and other tin compounds.

The production method of the above-mentioned copolymer may also include other steps than the above-mentioned reaction step. For example, an aging step, a neutralization step, a deactivation step of a polymerization initiator or a chain transfer agent, a dilution step, a drying step, a concentration step, a purification step, etc. are mentioned. These steps can be carried out by known methods.

2. Copolymer solution Moreover, this invention is also a copolymer solution characterized by containing the said copolymer and a protic polar solvent. The storage stability of the copolymer solution of the present invention is excellent. The above-mentioned copolymer has an acid group and an epoxy group as described above, and the reactivity of these groups is high, so that the above-mentioned copolymer is easy to harden at low temperature, but on the other hand, it is difficult to ensure storage stability. The present inventors found that by adding a protic polar solvent, the storage stability of the above-mentioned copolymer can be improved, so that both high solvent resistance and storage stability can be achieved. The reason why the storage stability of the above-mentioned copolymer is improved by adding a protonic polar solvent is not certain, but it is presumed that the reason is that in the above-mentioned copolymer, acid groups such as carboxyl groups are present at positions away from the main chain, whereby the protonic polar The solvent is relatively easy to hydrogen bond with the above-mentioned acid group, the anionicity of the acid group is reduced, and the reactivity of the acid group with the epoxy group is suppressed.

<Protic polar solvent> As said protic polar solvent, water, an alcohol-type solvent, an amine-type solvent, and a phenol-type solvent are mentioned, for example. Among them, the above-mentioned protic polar solvent is preferably an alcohol-based solvent.

Preferred examples of the alcohol-based solvent include saturated alcohols, and examples thereof include monofunctional alcohols (monoalcohols), polyhydric alcohols, ethylene glycol monoethers, and the like. Specific examples of the above-mentioned alcohol-based solvent include methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl ether Glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol mono-n-butyl ether, tripropylene glycol, tripropylene glycol mono-n-butyl ether Primary alcohols such as ethers; Isopropanol, 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, cyclohexanol, 2-heptanol, 3-heptanol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol monophenyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether or tripropylene glycol Secondary alcohols such as monomethyl ether; Tertiary alcohols such as tertiary butanol, tertiary pentanol, and tertiary hexanol, etc. Among them, the above-mentioned alcohol-based solvent is preferably a secondary alcohol or a tertiary alcohol in terms of suppressing the reactivity with epoxy groups and reducing the viscosity of the copolymer solution.

The carbon number of the alcohol-based solvent is preferably from 1 to 10, more preferably from 2 to 8, and further preferably from 3 to 6, in terms of relatively low boiling point and easy removal by heating.

As the above-mentioned alcohol-based solvent, propylene glycol monomethyl ether is particularly preferable.

As said amine type solvent, dieneethylamine, dimethylamine, oleylamine, etc. are mentioned, for example.

As said phenol type solvent, phenol, cresol, o-cresol, m-cresol, p-cresol, xylenol, etc. are mentioned, for example.

Only one type of the above-mentioned protic polar solvent may be used, or two or more types may be used in combination.

The boiling point of the protic polar solvent is preferably 70 to 170° C., more preferably 100 to 160° C., more preferably 100 to 160° C. 120～150℃.

The content of the protic polar solvent in the copolymer solution is preferably 10% by mass or more, more preferably 30% by mass, and still more preferably 40% by mass or more relative to 100% by mass of the solid content of the copolymer. In addition, the content of the protic polar solvent is preferably 1000 mass % or less, more preferably 300 mass % with respect to 100 mass % of the solid content of the copolymer, from the viewpoint of easy adjustment of the concentration in the curable resin composition. % or less, more preferably 200 mass % or less.

烷、乙二醇二甲醚、二乙二醇二甲醚等醚類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮類；乙酸乙酯、乙酸丁酯、丙二醇單甲醚乙酸酯、乙酸3-甲氧基丁酯等酯類；甲苯、二甲苯、乙基苯等芳香族烴類；氯仿；二甲基亞碸等。 In terms of stability, it is preferable that the above-mentioned copolymer solution further contains another solvent capable of hydrogen bonding in addition to the above-mentioned protic polar solvent. As said other solvent, N,N- dimethylformamide etc. are mentioned, for example. In addition, as a solvent for concentration adjustment, for example, tetrahydrofuran, dihydrofuran may be included.

alkane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and other ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; ethyl acetate, butyl acetate, Esters such as propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform;

When the above-mentioned copolymer solution contains other solvents than the above-mentioned protic polar solvent, the content of the above-mentioned protic polar solvent is preferably 5% by mass relative to 100% by mass of the total amount of the above-mentioned protic polar solvent and the above-mentioned other solvents. Above, more preferably 10 mass % or more, more preferably 20 mass % or more, preferably 99 mass % or less, more preferably 90 mass % or less, and still more preferably 80 mass % or less.

The above-mentioned copolymer solution can be prepared by mixing the above-mentioned protonic polar solvent obtained by purifying the copolymer obtained during the polymerization from a polymerization solution containing the above-mentioned copolymer, or by adding the above-mentioned protonic polar solvent to the above-mentioned polymerization solution containing the above-mentioned copolymer. prepared with polar solvents. When preparing by adding the above-mentioned protonic polar solvent to the polymerization solution containing the above-mentioned copolymer, the above-mentioned copolymer solution may also contain a polymerization solvent.

The above-mentioned copolymer solution may further contain other components. As another component, the component which improves the storage stability of the said copolymer, and the component which improves sclerosis|hardenability are mentioned. As a component which improves the storage stability of the said copolymer, an acid compound and a phosphoric acid derivative are mentioned, for example. As a component which improves the hardenability of the said copolymer, a basic compound is mentioned, for example. These components may be used appropriately according to the purpose, or may be used in combination.

<acid compound> The said copolymer solution may further contain the acid compound whose pKa is 4.2 or less. By making the said copolymer solution contain the acid compound whose pKa is 4.2 or less, the reaction of the acid group and epoxy group of the said copolymer can be suppressed, and the storage stability of the said copolymer can be improved further. The reason why the storage stability of the above-mentioned copolymer can be improved by containing an acid compound having a pKa of 4.2 or less is considered to be because the presence of an acid group having an acid strength stronger than that of the acid group-containing structural unit (B) that can form the above-mentioned copolymer The acid compound of the copolymer reduces the anionicity of the acid group in the copolymer, and the reactivity of the acid group and the epoxy group is suppressed. In addition, when a basic compound is present in the copolymer solution, the acid compound having a pKa of 4.2 or less captures the basic compound that forms a salt with the carboxyl group, and the nucleophilic force of the carboxyl group in the copolymer decreases, thereby inhibiting the acid group from interacting with the carboxyl group. Reactivity of epoxy groups.

The reason why the pKa is set to 4.2 or less is to set the pKa value of the monomer into which the structural unit (B) can be introduced or the acid group-containing monomer as a threshold value. Examples of the pKa value of the above monomers include acrylic acid (pKa 4.35), methacrylic acid (pKa 4.26), mono(2-acryloyloxyethyl) succinate (pKa 4.35), mono(2-succinic acid) - Methacryloyloxyethyl) ester (pKa 4.35) etc. The pKa of the acid compound is preferably 3 or less, more preferably 2 or less. The lower limit of the pKa of the acid compound is not particularly limited, but is preferably -3 or more, more preferably 0 or more.

pKa (acid dissociation constant) means the negative common logarithm (logarithm of the reciprocal) of the equilibrium constant Ka in the dissociation reaction in which hydrogen ions are released from an acid, especially the value in water at 25°C. For the value of pKa, for example, reference can be made to documents such as Handbook of Chemistry, Fundamentals II (Revision 5, Maruzen Co., Ltd.), and the value not described in the document can be calculated by the method described in the document.

Specific examples of the acid compound having a pKa of 4.2 or less include hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid, phosphinic acid, pyrophosphoric acid, and polyphosphoric acid. , sulfuric acid, sulfurous acid, thiosulfuric acid, dimethylsulfuric acid, diethylsulfurous acid, dipropylsulfurous acid, dibutylsulfurous acid, diphenylsulfurous acid, dimethylsulfuric acid, diethylsulfuric acid, Dipropyl sulfuric acid, dibutyl sulfuric acid, diphenyl sulfuric acid, benzenesulfinic acid, toluenesulfinic acid, naphthalenesulfinic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid Aromatic sulfonic acids such as acid, naphthalenesulfonic acid, diisopropylnaphthalenesulfonic acid, and diisobutylnaphthalenesulfonic acid; alkylsulfonic acids such as methylsulfonic acid, ethylsulfonic acid, and propylsulfonic acid; α-olefins Sulfonic acids, sulfonated polystyrenes, acrylic methyl-sulfonated styrene copolymers and derivatives of these.

The molecular weight of the acid compound is preferably 400 or less, more preferably 350 or less. The molecular weight of the acid compound is preferably 150 or more, more preferably 250 or more.

＜Phosphoric acid derivatives＞ The above-mentioned copolymer solution may also contain a phosphoric acid derivative. The storage stability of the said copolymer can be improved by making the said copolymer solution further contain a phosphoric acid derivative.

As said phosphoric acid derivative, a phosphate ester, a phosphite ester, phosphorous acid, a hypophosphorous acid, a phosphonic acid, and a phosphinic acid are preferably mentioned, and a phosphoric acid ester, a phosphonic acid, and a phosphinic acid are more preferable. As an ester group of the said phosphate ester or phosphite, an alkyl ester group, an aryl ester group, an aralkyl ester group, the ester group which has a polymerizable double bond, etc. are mentioned. As an alkyl group of the said alkyl ester group, a methyl group, an ethyl group, an octyl group, a 2-ethylhexyl group, etc. are mentioned. As an aryl group of the said aryl ester group, a phenyl group, a tolyl group, a naphthyl group, etc. are mentioned. A benzyl group etc. are mentioned as an aralkyl group of the said aralkyl ester group. As an ester group which has the said polymerizable double bond, a 2-acryloyloxyethyl ester group, a 2-methacryloyloxyethyl ester group, etc. are mentioned.

Specific examples of the above-mentioned phosphoric acid esters include, for example, monoalkyl phosphates such as methyl phosphate; dialkyl phosphates such as dibutyl phosphate; trimethyl phosphate, triethyl phosphate, tributyl phosphate, and triphosphate Octyl ester, tridecyl phosphate, tris(octadecyl) phosphate, distearyl neopentaerythritol diphosphate, tris(2-chloroethyl) phosphate, tris(2,3-dichlorophosphate) Trialkyl phosphate such as propyl) ester; Tricycloalkyl phosphate such as tricyclohexyl phosphate; Monoaryl phosphate; Diaryl phosphate; Triphenyl phosphate, tricresyl phosphate, tris(nonylbenzene phosphate) base), triaryl phosphates such as 2-ethylphenyl diphenyl phosphate; acid 2-methacryloyloxyethyl phosphate, acid 2-acryloyloxyethyl phosphate, acid 3-methacryloyl phosphate Phosphate esters containing an ester group having a polymerizable double bond, such as oxypropyl phosphate, polyoxyethylene glycol acid methacryloyl phosphate, and polyoxypropylene glycol acid methacryloyl phosphate. Specific examples of the above-mentioned phosphonic acid include alkylphosphonic acids such as methylphosphonic acid, arylphosphonic acids such as phenylphosphonic acid, and the like. Specific examples of the above-mentioned phosphinic acid include alkyl phosphinic acids such as methyl phosphinic acid, aryl phosphinic acids such as phenyl phosphinic acid, and the like.

Among them, as the above-mentioned phosphoric acid ester, a phosphoric acid ester containing the above-mentioned ester group having a polymerizable double bond is preferable. When a phosphoric acid ester containing the above-mentioned ester group having a polymerizable double bond is used, at the time of curing the curable resin composition containing the above-mentioned copolymer solution, a cross-linked structure is formed together with the above-mentioned copolymer or the polymerizable compound, thereby suppressing the In particular, the volatilization or dissolution of the contained components can suppress the occurrence of such problems as contamination of the reaction system or reduction of electrical insulation. The above-mentioned phosphoric acid ester preferably contains two or more polymerizable double bonds.

In the present invention, as the phosphoric acid ester containing the above-mentioned ester group having a polymerizable double bond, commercially available products can be used, for example, LIGHT ESTER P-1M, LIGHT ESTER P-2M (both are manufactured by Kyoeisha Chemical Co., Ltd.), Phosmer M (manufactured by Uni-Chemical Corporation) and the like. Among them, LIGHT ESTER P-2M is preferable.

The molecular weight of the phosphoric acid derivative is preferably 400 or less, more preferably 350 or less. When the molecular weight of the phosphoric acid derivative is 400 or less, the resin solid content at the time of addition can be reduced, and the storage stability can be further improved. In addition, the effect of improving the anionicity of the acid group and reducing the nucleophilic force becomes greater. The molecular weight of the phosphoric acid derivative is preferably 150 or more, more preferably 250 or more. When the molecular weight of the phosphoric acid derivative is 150 or more, the compatibility with the resin composition can be further improved.

The above-mentioned phosphoric acid derivative may be an acid compound having the above-mentioned pKa of 4.2 or less. That is, from the viewpoint of storage stability or compatibility, the copolymer solution of the present invention preferably contains an acid compound or a phosphoric acid derivative with a pKa of 4.2 or less, more preferably a phosphoric acid derivative with a pKa of 4.2 or less.

The content of the above-mentioned acid compound and phosphoric acid derivative is not particularly limited, and may be appropriately set according to the application or the blending of other components, and is preferably 100% by mass relative to the total solid content of the copolymer solution, usually 0.01-5 mass %, More preferably, it is 0.01-3 mass %, More preferably, it is 0.02-2 mass %. In addition, when the said acid compound and a phosphoric acid derivative are used together, the said content is the total amount of the said acid compound and a phosphoric acid derivative. In addition, in this specification, the "total amount of solid content" means the total amount of the components forming the hardened product (excluding the solvent etc. that volatilize when forming the hardened product).

The content of the acid compound and the phosphoric acid derivative is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the copolymer in the copolymer solution. In addition, when the said acid compound and a phosphoric acid derivative are used together, the said content is the total amount of the said acid compound and a phosphoric acid derivative.

When the above-mentioned copolymer solution further contains the following basic compound, the content of the above-mentioned acid compound and phosphoric acid derivative is preferably 50-200 mol%, more preferably 100 mol% of the basic compound used. It is 70 to 150 mol %, more preferably 80 to 120 mol %. By setting the content of the acid compound and the phosphoric acid derivative in the range of 0.5 to 2.0 molar equivalents relative to the basic compound, the storage stability of the copolymer is further improved, and the coloration of the cured product can be further suppressed. In addition, when the said acid compound and a phosphoric acid derivative are used together, the said content is the total amount of the said acid compound and a phosphoric acid derivative.

＜Basic compound＞ The said copolymer solution may further contain a basic compound. By containing the basic compound, when the copolymer is hardened, the crosslinking reaction proceeds well even under the low-temperature hardening conditions of 160° C. or lower, so that a hardened product with more excellent solvent resistance can be formed.

As said basic compound, the said basic compound is mentioned. Among them, amine-based compounds are preferred. In addition, as the above-mentioned basic compound, secondary amines, tertiary amines, heterocyclic amines, and phosphorus compounds are more preferable in terms of ease of evaporation and handling, which can suppress side reactions and suppress post-addition. From the viewpoint of increasing the molecular weight of the polymer, tertiary amine and triphenylphosphine are more preferred.

The content of the above-mentioned basic compound is not particularly limited, and may be appropriately set according to the application or the blending of other components, and is preferably 0.01 to 10% by mass relative to 100% by mass of the total solid content of the copolymer solution, and more Preferably it is 0.01-6 mass %, More preferably, it is 0.02-4 mass %.

Moreover, content of the said basic compound is preferable with respect to 100 mass parts of said copolymers, 0.01-20 mass parts is preferable, 0.1-10 mass parts is more preferable, 0.1-6 mass parts is still more preferable.

Furthermore, when the above-mentioned basic compound used as a catalyst during the synthesis of the above-mentioned copolymer (in addition reaction) remains in the copolymer solution after synthesizing the copolymer, the basic compound is added according to the residual amount by adding the basic compound. to adjust the content of the copolymer solution.

<Production method of copolymer solution> As a method for producing the above-mentioned copolymer solution, for example, a method comprising the steps of: adding an epoxy group-containing monomer represented by the above formula (a) and a hydroxyl group-containing monomer represented by the above formula (b1) The step of polymerizing the monomer components of the monomer (polymerization step); the polymer obtained in the above-mentioned polymerization step is reacted with the acid group-containing compound represented by the above formula (b2) or formula (b3) in the presence of a basic compound step (reaction step); and step (addition step) of adding an acid compound with a pKa of 4.2 or less and a protic polar solvent. That is, a method for producing a copolymer solution is also one of the present invention, which is characterized by comprising: mixing an epoxy group-containing monomer represented by formula (a) and a hydroxyl group-containing monomer represented by formula (b1). The step of polymerizing the monomer component of It is the step of acid compound and protic polar solvent below 4.2.

As said polymerization process, the process similar to the process (1) in the manufacturing method of the said copolymer can be mentioned.

As the above-mentioned reaction step, the same method as the method of step (2) in the method for producing the above-mentioned copolymer in the presence of a basic compound can be exemplified. Specific examples of the acid group-containing compound and the basic compound represented by the above formula (b2) or formula (b3) include the same compounds as the above-mentioned acid group-containing compound and basic compound.

The acid compound with a pKa of 4.2 or less and the protic polar solvent used in the above-mentioned addition step are as described above, respectively.

3. Curable resin composition The copolymer of the present invention and the copolymer solution may be combined with other components to form a curable resin composition. Since the said curable resin composition contains the copolymer of this invention, even under low temperature hardening conditions, the hardened|cured material excellent in solvent resistance can be formed. Moreover, when the said curable resin composition contains the said copolymer solution, storage stability becomes more excellent. Moreover, such a curable resin composition containing the said copolymer or a copolymer solution is also one of preferable aspects of this invention.

In the curable resin composition, the content of the above-mentioned copolymer is not particularly limited, and can be appropriately set according to the application or the blending of other components. For example, it is 100 mass relative to the total solid content of the curable resin composition. %, preferably 5 mass % or more, more preferably 10 mass % or more, more preferably 15 mass % or more, and more preferably 80 mass % or less, more preferably 75 mass % or less, and more preferably 70 mass % mass % or less. In addition, in this specification, "solid content total amount" means the total amount of the components which form a hardened|cured material (excluding the solvent etc. which volatilize at the time of hardened|cured material formation).

It is preferable that the said curable resin composition contains the said protic polar solvent from the point that the stability as a composition becomes favorable. The content of the above-mentioned protic polar solvent in the above-mentioned curable resin composition is preferably 10% by mass or more relative to 100% by mass of the solid content of the above-mentioned copolymer in terms of ensuring the stability of the curable resin composition. , more preferably 30 mass % or more, still more preferably 40 mass % or more, and more preferably 3000 mass % or less, more preferably 1000 mass % or less.

In terms of securing the stability of the curable resin composition, the content of the above-mentioned protic polar solvent in the curable resin composition is preferably 1 mass % relative to 100 mass % of the solid content of the curable resin composition. % or more, more preferably 5 mass % or more, more preferably 10 mass % or more, and more preferably 400 mass % or less, more preferably 300 mass % or less, and still more preferably 200 mass % or less.

The said curable resin composition may further contain various components, such as a polymerizable compound and a polymerization initiator. As for various components, such as a polymerizable compound and a polymerization initiator, the same components as the following photosensitive resin composition, etc. are mentioned. The photosensitive resin composition will be described as an example of a preferable form of the above-mentioned curable resin composition.

3-1. Photosensitive resin composition The copolymer or copolymer solution of the present invention can be further combined with a polymerizable compound and a photopolymerization initiator to form a photosensitive resin composition. Since the said photosensitive resin composition contains the said copolymer, even under the low temperature hardening conditions of 160 degrees C or less, for example, about 90 degreeC, the hardened|cured material excellent in solvent resistance can be formed. In addition, since a polymerizable compound is further contained, a cured product excellent in various physical properties such as curability, adhesion to a base material, surface hardness, and heat resistance can be formed. Moreover, the photosensitive resin composition containing the said copolymer or a copolymer solution, a polymerizable compound, and a photopolymerization initiator is also one of this invention.

In the photosensitive resin composition of the present invention, the content of the above-mentioned copolymer is not particularly limited, and can be appropriately set according to the application or the blending of other components, for example, relative to the total solid content of the photosensitive resin composition. 100 mass %, preferably 5 mass % or more, more preferably 10 mass % or more, more preferably 15 mass % or more, and preferably 80 mass % or less, more preferably 75 mass % or less, and furthermore It is 70 mass % or less.

<Polymerizable compound> The above-mentioned polymerizable compounds are polymerizable unsaturated bonds (also called polymerizable unsaturated groups) that can be polymerized by irradiation with active energy rays such as free radicals, electromagnetic waves (such as infrared rays, ultraviolet rays, X-rays, etc.), and electron beams. As a low molecular weight compound, the monofunctional compound which has one polymerizable unsaturated group in a molecule|numerator, and the polyfunctional compound which has two or more polymerizable unsaturated groups are mentioned, for example.

Examples of the monofunctional compound include: N-substituted maleimide-based monomers; (meth)acrylates; (meth)acrylamides; unsaturated monocarboxylic acids; unsaturated polycarboxylic acids Acids; unsaturated monocarboxylic acids extended between unsaturated groups and carboxyl groups; unsaturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; Unsaturated isocyanates, etc. As these, for example, the same compounds as those listed as the monomer components of the above-mentioned copolymers can be mentioned. Moreover, the monomer etc. which have an active methylene group or an active methine group can also be used.

As said polyfunctional compound, the following compounds etc. are mentioned, for example. Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate base) acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate Bifunctional (meth)acrylate compounds such as (meth)acrylates;

Trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, glycerol tri(meth)acrylate, neotaerythritol tri(meth)acrylate, new Pentaerythritol tetra(meth)acrylate, Dipiveaerythritol penta(meth)acrylate, Dipiveaerythritol hexa(meth)acrylate, Tripivalerythritol hepta(meth)acrylate, Trinepentaerythritol octa(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, ethylene oxide addition di-trimethylolpropane tetra(methyl) Acrylates, ethylene oxide addition neotaerythritol tetra(meth)acrylate, ethylene oxide addition dipivoerythritol hexa(meth)acrylate, propylene oxide addition trimethylolpropane Tri(meth)acrylate, propylene oxide addition di-trimethylolpropane tetra(meth)acrylate, propylene oxide addition neotaerythritol tetra(meth)acrylate, propylene oxide addition Dipivalerythritol hexa(meth)acrylate, ε-caprolactone addition trimethylolpropane tri(meth)acrylate, ε-caprolactone addition di-trimethylolpropane tetra(meth)acrylate base) acrylate, ε-caprolactone addition neopentaerythritol tetra (meth)acrylate, ε-caprolactone addition dipivaloerythritol hexa (meth)acrylate, dipepentaerythritol penta Acrylate succinic acid modified product, Neotaerythritol triacrylate succinic acid modified product, Dipivalerythritol pentaacrylate phthalic acid modified product, Neotaerythritol triacrylate phthalic acid modified product, The following Mode:

Polyfunctional (meth)acrylate compounds with three or more functionalities, such as the modified substance of dinepentaerythritol hexaacrylate represented;

Ethylene Glycol Divinyl Ether, Diethylene Glycol Divinyl Ether, Polyethylene Glycol Divinyl Ether, Propylene Glycol Divinyl Ether, Butylene Glycol Divinyl Ether, Hexylene Glycol Divinyl Ether, Bisphenol A Alkylene Oxide Divinyl Ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, di-trimethylolpropane tetravinyl ether, glycerol trivinyl ether, neopentaerythritol tetravinyl ether, dipepaerythritol Pentavinyl ether, dipeptaerythritol hexavinyl ether, ethylene oxide addition trimethylolpropane trivinyl ether, ethylene oxide addition di-trimethylolpropane tetravinyl ether, ethylene oxide addition Into polyfunctional vinyl ethers such as neopentaerythritol tetravinyl ether, ethylene oxide addition dipeptaerythritol hexavinyl ether, etc.;

2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2 (meth)acrylate - Vinyloxypropyl, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, (meth)acrylate ) 6-vinyloxyhexyl acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2- (meth)acrylate (Meth)acrylates containing vinyl ether groups such as (vinyloxyethoxy)ethyl ester and (meth)acrylate 2-(vinyloxyethoxyethoxyethoxy)ethyl ester;

Ethylene Glycol Diallyl Ether, Diethylene Glycol Diallyl Ether, Polyethylene Glycol Diallyl Ether, Propylene Glycol Diallyl Ether, Butylene Glycol Diallyl Ether, Hexylene Glycol Diallyl Ether, Bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, di-trimethylolpropane tetraallyl ether, glycerol triallyl ether, neopentyl Tetraol tetraallyl ether, dipeptaerythritol pentaallyl ether, dipeptaerythritol hexaallyl ether, ethylene oxide addition trimethylolpropane triallyl ether, ethylene oxide addition two - Multifunctional allyl ethers such as trimethylolpropane tetraallyl ether, ethylene oxide addition neopentaerythritol tetraallyl ether, ethylene oxide addition dipepaerythritol hexaallyl ether;

Allyl-containing (meth)acrylates such as (meth)acrylate; trimeric isocyanate tris(acryloyloxyethyl), trimeric isocyanate tris(methacryloyloxy) Ethyl ethyl) ester, alkylene oxide addition trimeric isocyanate tris (acryloyloxyethyl) ester, alkylene oxide addition trimeric isocyanate tris (methacryloyloxyethyl) ester, etc. Trimeric isocyanates containing polyfunctional (meth)acryloyl groups; trimeric isocyanates containing polyfunctional allyl groups such as triallyl isocyanate; using toluene diisocyanate, isophorone It is obtained by the reaction of polyfunctional isocyanates such as diisocyanate and stubble diisocyanate with hydroxyl-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Polyfunctional (meth)acrylates; polyfunctional aromatic vinyls such as divinylbenzene, etc. These polymerizable compounds may be used alone or in combination of two or more. However, although a polymer having a vinyl ether group in its side chain improves the curability of the resin composition, it may lower the storage stability. Therefore, in terms of storage stability, the above-mentioned photosensitive resin composition is preferably It does not contain a polymer having a vinyl ether group in its side chain.

Among the above-mentioned polymerizable compounds, it is preferable to use a polyfunctional polymerizable compound from the viewpoint of further improving the curability of the photosensitive resin composition. As a functional number of the said polyfunctional polymerizable compound, 3 or more are preferable, and 4 or more are more preferable. Moreover, 10 or less are preferable and, as for the said functional number, 8 or less are more preferable. Moreover, although it does not specifically limit as molecular weight of the said polymerizable compound, From a viewpoint of handleability, for example, it is preferable that it is 2000 or less.

Among the above-mentioned polyfunctional polymerizable compounds, from the viewpoints of reactivity, economical efficiency, availability, etc., polyfunctional (meth)acrylate compounds, polyfunctional (meth)acrylate amine ester compounds, polyfunctional (meth)acrylate compounds, Compounds having a (meth)acryloyl group, such as a (meth)acryloyl trimeric isocyanate compound, are more preferably polyfunctional (meth)acrylate compounds. By containing the compound which has a (meth)acryloyl group, the photosensitive resin composition can be made into one which is more excellent in photosensitivity and hardenability, and the hardened|cured material of higher hardness and high transparency can be obtained. As said polyfunctional polymerizable compound, it is more preferable to use the polyfunctional (meth)acrylate compound of trifunctional or more.

Only one type of the above-mentioned polymerizable compound may be used, or two or more types may be used in combination.

In the photosensitive resin composition of the present invention, the content of the polymerizable compound is not particularly limited as long as the content of the polymerizable compound is within the range in which the effects of the present invention are exhibited, and it may be appropriately set, but the photosensitive resin composition can be appropriately set. The viscosity is preferably 5 to 60 mass %, more preferably 10 to 50 mass % with respect to 100 mass % of the total solid content of the photosensitive resin composition.

<Photopolymerization initiator> As the photopolymerization initiator, a radically polymerizable photopolymerization initiator is preferably used. The radically polymerizable photopolymerization initiator is one that generates polymerization initiation radicals by irradiation with active energy rays such as electromagnetic waves or electron beams.

啉基丙烷-1-酮（「Irgacure 907」、BASF公司製造）、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮-1（「Irgacure 369」、BASF公司製造）、2-二甲基胺基-2-(4-甲基-苄基)-1-(4-

啉-4-基-苯基)-丁烷-1-酮（「Irgacure 379」、BASF公司製造）等胺基酮系化合物；2,2-二甲氧基-1,2-二苯基乙烷-1-酮（「Irgacure 651」、BASF公司製造）、苯基乙醛酸性甲酯（「DAROCUR MBF」、BASF公司製造）等二苯乙二酮縮酮系化合物；1-羥基-環己基-苯基-酮（「Irgacure 184」、BASF公司製造）、2-羥基-2-甲基-1-苯基-丙烷-1-酮（「DAROCUR1173」、BASF公司製造）、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮（「Irgacure 2959」、BASF公司製造）、2-羥基-1-{4-[4-(2-羥基-2-甲基-丙醯基)-苄基]-苯基}-2-甲基-丙烷-1-酮（「Irgacure 127」、BASF公司製造）、[1-羥基-環己基-苯基-酮＋二苯甲酮]（「Irgacure 500」、BASF公司製造）等羥基酮系化合物等；以及日本特開2013-227485號公報段落[0084]～[0086]所例示之其他烷基苯酮系化合物；1,2-辛烷二酮,1-[4-(苯硫基)苯基]-,2-(O-苯甲醯基肟)（「OXE01」、BASF公司製造）、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)（「OXE02」、BASF公司製造）、1,2-辛烷二酮,1-[4-(苯硫基)-,2-,(O-苯甲醯基肟)],乙酮（「OXE03」、BASF公司製造）、1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)（「OXE04」、BASF公司製造）等肟酯系化合物；二苯甲酮系化合物；安息香系化合物；9-氧硫

系化合物；鹵甲基化三𠯤系化合物；鹵甲基化

二唑系化合物；聯咪唑系化合物；二茂鈦系化合物；苯甲酸酯系化合物；吖啶系化合物等；膦氧化物系化合物等。其中，較佳為胺基酮系化合物、肟酯系化合物。 上述光聚合起始劑可單獨使用1種，亦可將2種以上組合使用。 Specific examples of the above-mentioned photopolymerization initiators include, for example: 2-methyl-1-[4-(methylthio)phenyl]-2-

Linopropan-1-one ("Irgacure 907", manufactured by BASF Corporation), 2-benzyl-2-dimethylamino-1-(4-

Linophenyl)-butanone-1 ("Irgacure 369", manufactured by BASF Corporation), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-

Lino-4-yl-phenyl)-butan-1-one ("Irgacure 379", manufactured by BASF Corporation) and other amino ketone compounds; 2,2-dimethoxy-1,2-diphenylethyl Alkan-1-one ("Irgacure 651", manufactured by BASF Corporation), phenylglyoxal acid methyl ester ("DAROCUR MBF", manufactured by BASF Corporation) and other diphenylethanal ketal compounds; 1-Hydroxy-cyclohexyl -Phenyl-one ("Irgacure 184", manufactured by BASF Corporation), 2-hydroxy-2-methyl-1-phenyl-propan-1-one ("DAROCUR1173", manufactured by BASF Corporation), 1-[4- (2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (“Irgacure 2959”, manufactured by BASF Corporation), 2-hydroxy-1-{4-[ 4-(2-Hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one ("Irgacure 127", manufactured by BASF Corporation), [1-hydroxyl -Cyclohexyl-phenyl-ketone+benzophenone] ("Irgacure 500", manufactured by BASF Corporation) and other hydroxyketone-based compounds, etc.; Other alkyl phenone compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzyl oxime) ("OXE01", BASF manufactured by the company), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) ( "OXE02", manufactured by BASF Corporation), 1,2-octanedione, 1-[4-(phenylthio)-,2-,(O-benzyl oxime)], ethyl ketone ("OXE03" , manufactured by BASF Corporation), 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (“ Oxime ester-based compounds such as OXE04", manufactured by BASF Corporation); Benzophenone-based compounds; Benzoin-based compounds; 9-oxosulfur

Series compounds; Halomethylated tris-series compounds; Halomethylated

Diazole-based compounds; biimidazole-based compounds; titanocene-based compounds; benzoate-based compounds; acridine-based compounds, etc.; phosphine oxide-based compounds, and the like. Among them, amino ketone-based compounds and oxime ester-based compounds are preferred. The said photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the above-mentioned photopolymerization initiator is not particularly limited as long as the effect of the present invention is exhibited, and can be appropriately set, for example, 100% by mass relative to the total solid content of the photosensitive resin composition of the present invention , preferably 0.3 to 20 mass %, more preferably 0.5 to 10 mass %, still more preferably 1 to 8 mass %.

<Photoacid generator> It is preferable that the photosensitive resin composition of this invention further contains a photoacid generator. By further containing a photoacid generator, the curability of the photosensitive resin composition can be further improved. The above-mentioned photoacid generator is a compound that generates acid by exposure to active energy rays such as radiation, and examples thereof include strong acids such as toluenesulfonic acid and boron tetrafluoride, strontium salts, ammonium salts, phosphonium salts, iodonium salts, or selenium salts. Onium salts such as salts; iron-allene complexes; silanol-metal chelate complexes; Sulfonic acid derivatives such as acylbenzylmethanes, imidates, benzoin sulfonates, etc.; organic halogen compounds, etc.

The content of the photoacid generator is preferably 0.3 to 20 mass %, more preferably 0.5 to 10 mass %, and further preferably 1 to 8 mass % with respect to 100 mass % of the total solid content of the photosensitive resin composition. %.

＜Other ingredients＞ In addition to the above-mentioned components, the photosensitive resin composition of the present invention may contain other components as necessary. Examples of the above-mentioned other components include: solvents; colorants (pigments, dyes); dispersants; heat-resistant improvers; leveling agents; development aids; inorganic fine particles such as silica fine particles; and other coupling agents; fillers, epoxy resins, phenol resins, polyvinyl phenol and other thermosetting resins; multifunctional thiol-based compounds and other hardening aids; plasticizers; polymerization inhibitors; ultraviolet absorbers; antioxidants; matting agents ; defoaming agent; antistatic agent; slipping agent; surface modifier; thixotropic agent; thixotropic auxiliary; quinonediazide compound; polyphenol compound; cationic polymerizable compound; acid generator, etc. . These may be used individually by 1 type, and may be used in combination of 2 or more types. These other components may be appropriately selected from those known to be used, and the usage amount thereof may be appropriately set. For example, when using the said photosensitive resin composition for a color filter application, it is preferable that the said photosensitive resin composition contains a coloring material.

<Preparation of photosensitive resin composition> The method for preparing the photosensitive resin composition of the present invention is not particularly limited, and a known method may be used. For example, a method of mixing and dispersing the above-mentioned components using various mixers or dispersers is exemplified. The mixing and dispersing steps are not particularly limited, and may be performed by known methods. In addition, other steps normally performed may be further included. When the said photosensitive resin composition contains a colorant, it is preferable to prepare it through a well-known process, such as the dispersion|distribution process process of a colorant.

<hardened product> The cured product obtained by curing the copolymer, the copolymer solution or the photosensitive resin composition (curable resin composition) of the present invention has excellent solvent resistance. Such a copolymer, a copolymer solution or a cured product of the photosensitive resin composition is also one of the present inventions.

When the above-mentioned cured product is a cured film, the film thickness thereof is preferably 0.1 μm or more. When the said film thickness is 0.1 micrometer or more, more excellent solvent resistance can be exhibited. The above-mentioned film thickness is more preferably 0.5 μm or more, and still more preferably 1 μm or more. The upper limit of the film thickness is not particularly limited, and may be appropriately set according to the purpose and application of the cured film.

The method for obtaining the above-mentioned cured product is not particularly limited, and a known method may be used, and examples thereof include the following methods: The product solution or the photosensitive resin composition is coated or molded on the base material and cured to obtain a cured product.

If the copolymer, copolymer solution or photosensitive resin composition of the present invention is used, a cured product excellent in solvent resistance can be formed even under low temperature curing conditions. As a method for producing such a cured product, for example, a method comprising the steps of: applying the above-mentioned photosensitive resin composition to a substrate to form a coating film; The step of irradiating; and the step of heating the coated film irradiated with light below 160°C.

The above-mentioned base material is not particularly limited, and may be appropriately selected according to the purpose or application, and examples thereof include base materials made of various materials such as glass plates and plastic plates.

There is no restriction|limiting in particular as a method to apply|coat the said photosensitive resin composition, and to form a coating film, Well-known methods, such as spin coating, slot coating, roll coating, and casting coating, can be used. In the said manufacturing method, after apply|coating the said photosensitive resin composition on a base material, it is preferable to dry a coating material, and it is preferable to form a coating film. The above-mentioned drying can be performed by a known method, and specifically, it can be performed by the same method as the drying method described in the "arrangement step" of the following "<Method for producing a color filter>".

The above-mentioned manufacturing method includes the step of irradiating the above-mentioned coating film with light after forming the coating film. The method of irradiating the formed coating film with light is not particularly limited, and a known method can be used. Specifically, the following "<Method for producing a color filter>" can be used. The method described in "Irradiation step" was carried out in the same manner.

When light irradiation is performed to the said coating film, light irradiation can be performed through a photomask. As the photomask, a photomask in which a light shielding portion is formed in accordance with a target pattern can be used. In the case of performing light irradiation through a photomask, it is preferable to perform a development step afterward. By carrying out the developing step, a target pattern can be formed on the coating film. The development method is not particularly limited, and can be performed by a known method. Specifically, it can be performed by the same method as the method described in the "development step" of the following "<Method for producing a color filter>".

Moreover, the said manufacturing method includes the process of heating the coating film irradiated with light below 160 degreeC. Since the above-mentioned production method uses the above-mentioned photosensitive resin composition, the heating step (post-curing step) after light irradiation can be performed under relatively low temperature conditions such as 160° C. or lower. The heating temperature is preferably 155°C or lower, more preferably 150°C or lower. The lower limit of the heating temperature is preferably 70°C or higher, more preferably 90°C or higher, from the viewpoint of maintaining curability. The above-mentioned heating method other than the temperature is not particularly limited, and can be performed by a known method. For example, it can be performed by the same method as the method described in the "heating step" of the following "<Method for producing a color filter>". .

＜Use＞ The copolymer of the present invention, the copolymer solution, and the photosensitive resin composition (curable resin composition) containing the same undergo sufficient curing reaction even under low-temperature curing conditions of 160° C. or lower, for example, about 90° C., so that A hardened product with excellent solvent resistance can be formed. Therefore, it can be preferably used for applications requiring sufficient hardening under low temperature conditions or applications requiring solvent resistance.

Specifically, the copolymer, the copolymer solution, and the photosensitive resin composition of the present invention can be preferably used, for example, for liquid crystal-organic EL-quantum dot-micro LED liquid crystal display devices, solid-state imaging elements, and touch-panel display devices. Color filters, black matrices, photospacers, black column spacers, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, insulating films, films, organic protective films, etc. used in devices, etc. The use of various optical components or components of electro-mechanical-electronic equipment. Among them, it can be preferably used for color filter applications. The photosensitive resin composition of the present invention can be preferably used as an optical material, and can also be preferably used as a negative type.

3. Color filter The color filter which has the hardened|cured material of the said photosensitive resin composition on a board|substrate is also one of preferable forms of this invention. In the above-mentioned color filter, the cured product formed by the above-mentioned photosensitive resin composition is especially suitable as a black matrix or a segment that needs to be colored for each pixel such as red, green, blue, and yellow, but is also suitable as a photosensitive material. Spacers, protective layers, barrier ribs for alignment control, etc. do not necessarily require colored segments.

Examples of substrates used for the above-mentioned color filters include glass substrates such as white plate glass, blue plate glass, alkali-strengthened glass, and silica-coated blue plate glass; Sheets, films or substrates made of thermoplastic resins such as ring-opening polymers of cyclic olefins or their hydrides; sheets, films or substrates made of thermosetting resins such as epoxy resins and unsaturated polyester resins; aluminum plates, Metal substrates such as copper plates, nickel plates, stainless steel plates; ceramic substrates; semiconductor substrates with photoelectric conversion elements; glass substrates with color layers on the surface (such as color filters for LCD), etc. Among them, in terms of heat resistance, a glass substrate or a sheet, film, or substrate made of a heat-resistant resin is preferable. Moreover, it is preferable that the said board|substrate is a transparent board|substrate. In addition, corona discharge treatment, ozone treatment, chemical treatment with a silane coupling agent, etc. may be performed on the above-mentioned substrate as necessary.

<Manufacturing method of color filter> In order to obtain the above-mentioned color filter, for example, it is preferable to adopt the following manufacturing method: for a pixel of one color (ie, a pixel of each color), a step including disposing the above-mentioned photosensitive resin composition on a substrate (also referred to as an disposition step), The step of irradiating light to the photosensitive resin composition disposed on the substrate (also referred to as a light irradiation step), the step of developing treatment with a developer (also referred to as a development step), and the step of heat treatment (also referred to as for the heating step), and repeat the same method for each color. Furthermore, the order in which the pixels of each color are formed is not particularly limited.

(1) Arrangement step (preferably coating step) The above-mentioned configuration step is preferably performed by coating. As a method of apply|coating the said photosensitive resin composition on a board|substrate, a spin coater, a slit coater, a roll coater, a cast coater etc. are mentioned, for example; Any method can be used suitably. In the said arrangement|positioning process, it is also preferable to dry a coating film after apply|coating the said photosensitive resin composition on a board|substrate. Drying of the coating film can be performed using, for example, a hot plate, an IR oven, a convection oven, or the like. The drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of hardening component, the thickness of the film, and the performance of the dryer. Usually, it is preferably performed at a temperature of 50 to 160° C. for 10 seconds to 300 seconds.

(2) Light irradiation step As the light source of the active light used in the above-mentioned light irradiation step, for example, xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, fluorescent lamps are used. Light sources such as light lamps; laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, semiconductor lasers, etc. Moreover, as a method of an exposure machine, a proximity exposure method, a mirror projection method, and a stepper method can be mentioned, and a proximity exposure method can be preferably used. Furthermore, in the irradiation step of the active energy light, the active energy light can also be irradiated through a specific mask pattern depending on the application. In this case, the exposed portion is hardened, and the hardened portion becomes insoluble or hardly soluble in the developing solution.

(3) Development step The said developing process is a process of forming a pattern by removing an unexposed part by performing a developing process with a developing solution after the said light irradiation process. Thereby, a patterned cured film can be obtained. The development treatment can usually be performed at a development temperature of 10 to 50° C. by means of immersion development, spray development, brush development, and ultrasonic development.

The developer used in the development step is not particularly limited as long as it dissolves the photosensitive resin composition. Usually, an organic solvent or an alkaline aqueous solution is used, and a mixture of these can also be used. In addition, when an alkaline aqueous solution is used as a developing solution, it is preferable to wash with water after image development. As the organic solvent or the alkaline aqueous solution, the same ones as those described in JP-A No. 2015-157909 can be mentioned.

(4) Heating step The heating step described above is a step (also referred to as a “post-curing step”) of further curing the exposed portion (hardened portion) by firing after the developing step. Examples include a step of post-exposure using a light source such as a high-pressure mercury lamp with a light intensity of 0.5 to 5 J/cm ² , or a step of post-heating at a temperature of 60 to 200° C. for 10 seconds to 120 minutes. By performing such a post-hardening step, the hardness and adhesiveness of the patterned cured film can be further strengthened. The above-mentioned heating step is generally performed at a temperature of about 200-260°C. If the above-mentioned photosensitive resin composition is used, sufficient curing can be performed at a relatively low temperature of 200°C or lower, preferably 160°C or lower. Therefore, the properties retained by the substrate or the cured product are not impaired, and one having excellent solvent resistance can be obtained.

In the above-mentioned heating step, the heating temperature is preferably 160°C or lower, more preferably 155°C or lower, and still more preferably 150°C or lower. In addition, the heating temperature is preferably 70°C or higher, more preferably 90°C or higher, and still more preferably 95°C or higher.

Although the heating time in the said heating process is not specifically limited, For example, it is preferable to set it as 5-60 minutes. In addition, the heating method is also not particularly limited, and for example, it can be performed using a heating device such as a hot plate, a convection oven, and a high frequency heater.

It is preferable that the film thickness of the cured film obtained by the said heating process (that is, the cured coating film obtained by thermosetting the said photosensitive resin composition) is 0.1-20 micrometers. The above-mentioned film thickness is more preferably 0.5 to 15 μm, still more preferably 1 to 10 μm.

4. Display device A display device having the above-mentioned color filter is also one of the preferred forms in the present invention. Moreover, the member for display apparatuses and the display apparatus which have the hardened|cured material of the said photosensitive resin composition are also included in the preferable embodiment of this invention. The cured product (cured film) formed from the above-mentioned photosensitive resin composition is stable, has excellent adhesion to substrates and the like, has high hardness, exhibits high smoothness, and has high transmittance, and is therefore particularly preferred. It can be used as a transparent member, and can also be used as a protective film or an insulating film in various display devices.

As the above-mentioned display device, for example, a liquid crystal display device, a solid-state imaging element, a touch panel type display device, or the like is preferable. Furthermore, when using the above-mentioned cured product (cured film) as a member for a display device, the member may be a film-like single-layer or multi-layer member composed of the above-mentioned cured film, or may be a single-layer or multi-layer member of the above-mentioned cured film. Further, the member may be a member in which another layer is combined, or may be a member including the above-mentioned cured film in the configuration.

As described above, the copolymer, the copolymer solution, and the photosensitive resin composition (curable resin composition) of the present invention can form cured products excellent in solvent resistance even under low-temperature curing conditions. The copolymer, the copolymer solution, and the photosensitive resin composition of the present invention can be used as various optical components used in liquid crystal-organic EL-quantum dot-micro LED liquid crystal display devices, solid-state imaging devices, touch panel display devices, etc. As a constituent member, it is preferably used for various applications such as electromechanical and electronic equipment. Example

Hereinafter, the present invention will be described in more detail by showing examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, "part" means "mass part", and "%" means "mass %".

In this Example, the measurement of various physical properties etc. was performed by the following method. (1) Weight average molecular weight (Mw) The weight average molecular weight was measured by GPC (gel permeation chromatography) method based on HLC-8220GPC (manufactured by Tosoh Corporation) and column: TSKgel SuperHZ M-M (manufactured by Tosoh Corporation) using polystyrene as a standard substance and tetrahydrofuran as a precipitate. .

(2) Solid content About 1 g of the copolymer solution was weighed and placed in an aluminum cup, and about 3 g of acetone was added to dissolve it, and then it was naturally dried at room temperature. Next, using a hot air dryer (trade name: PHH-101, manufactured by ESPEC), after drying at 140° C. under vacuum for 1.5 hours, it was left to cool in a desiccator, and the mass was measured. The solid content (mass %) of the polymer solution was calculated from the mass reduction.

(3) Acid value 3 g of the copolymer solution was accurately weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated using a 0.1 N aqueous KOH solution as a titrant. The titration was performed using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value (mgKOH/g) per 1 g of the solid content was determined from the acid value of the solution and the solid content of the solution.

(4) Epoxy equivalent (g/equivalent) It was calculated|required by dividing the mass (g) of the solid content of the copolymer by the mole number (mol) of epoxy groups contained in the copolymer.

(5) Double bond equivalent (g/equivalent) It was obtained by dividing the mass (g) of the solid content of the copolymer by the double bond amount (mol) of the copolymer.

(6) Solvent resistance The photosensitive resin composition was spin-coated on a 5 cm square glass substrate, dried at 100°C for 3 minutes, exposed to light at 200 mJ using a high-pressure mercury lamp, and heat-treated at 90°C or 110°C for 40 minutes (post-curing). ) to obtain a cured film with a thickness of 2 μm. Next, the cured film was immersed in 20 g of 1-methyl-2-pyrrolidone (NMP) at 40° C. for 10 minutes, and then taken out, and a spectrophotometer UV3100 was used for the immersion liquid (NMP) after taking out the cured film. (manufactured by Shimadzu Corporation) The absorbance was measured and evaluated according to the following criteria. The larger the value of the absorbance, the more the colorant eluted into the immersion liquid, and it was evaluated that the solvent resistance of the photosensitive resin composition was low. (Evaluation Criteria) ◎: The absorbance value is less than 0.2 ○: The value of absorbance is 0.2 or more and less than 0.3 △: The value of absorbance is 0.3 or more and less than 0.4 ×: The value of absorbance is 0.4 or more ××: Film peeled off

(7) Solvent resistance (Examples 20 to 23) The photosensitive resin composition was spin-coated on a 5 cm square glass substrate, dried at 90°C for 2 minutes, exposed to light at 100 mJ using a high-pressure mercury lamp, and heat-treated at 90°C for 30 minutes (post-curing) to obtain a film Hardened film with a thickness of 2 μm. Next, the cured film was immersed in 20 g of the immersion solvent described in Table 5 at 30°C for 5 minutes, and then taken out, and the absorbance was measured using a spectrophotometer UV3100 (manufactured by Shimadzu Corporation) about the immersion solvent after taking out the cured film.

(8) Viscosity The viscosity of the copolymer solution was measured at 25°C using a viscometer (VISCOMETER TV-22, manufactured by Toki Sangyo Co., Ltd.).

(9) Residual film rate The remaining film ratio was calculated by measuring the weight of the film before and after the evaluation of the solvent resistance in the above (7). Specifically, the film weight before solvent resistance evaluation was calculated by using the glass substrate as the tare weight. Then, the residual film ratio was calculated by dividing the film weight after solvent resistance evaluation by the film weight before evaluation.

(Manufacturing example 1) Preparation of copolymer solution A-1 (SAH adduct solution of HEMA-GMA copolymer) After adding 185.3 parts of propylene glycol monomethyl ether acetate to the reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port, it heated up to 90 degreeC after nitrogen substitution. On the other hand, 30.0 parts of 2-hydroxyethyl methacrylate, 70.0 parts of glycidyl methacrylate, 30 parts of propylene glycol monomethyl ether acetate, and 30 parts of propylene glycol monomethyl ether acetate were prepared in a beaker serving as a dropping tank (A). 2.0 parts of tertiary butyl 2-ethylhexanoate ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) was stirred and mixed, and n-dodecyl sulfide was prepared in the dropping tank (B). 2.0 parts of alcohol and 18.0 parts of propylene glycol monomethyl ether acetate were stirred and mixed. After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 11.5 parts of succinic anhydride, 0.33 parts of triethylamine as a catalyst, 189 parts of dimethyl carbonate, and 29.6 parts of propylene glycol monomethyl ether acetate were added and reacted at 40° C. for 10 hours, A copolymer solution A-1 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing example 2) Preparation of copolymer solution A-2 (SAH adduct solution of BzMI-CHMA-HEMA-GMA copolymer) After adding 172.0 parts of propylene glycol monomethyl ether acetate to the reaction tank provided with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port and nitrogen-substituting, it heated up to 90 degreeC. On the other hand, 10.0 parts of N-benzylmaleimide, 43.6 parts of cyclohexyl methacrylate, and 30.0 parts of 2-hydroxyethyl methacrylate were prepared in a beaker serving as a dropping tank (A). , 16.4 parts of glycidyl methacrylate, 30 parts of propylene glycol monomethyl ether acetate, 2.0 parts of 3-butyl peroxide 2-ethylhexanoate ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) What was stirred and mixed was prepared by stirring and mixing 2.0 parts of n-dodecyl mercaptan and 31.33 parts of propylene glycol monomethyl ether acetate in the dropping tank (B). After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 11.5 parts of succinic anhydrides, 0.33 parts of triethylamine as a catalyst, and 29.0 parts of propylene glycol monomethyl ether acetate were reacted at 60° C. for 10 hours to obtain a copolymer solution A-2. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing example 3) Preparation of copolymer solution A-3 (SAH adduct solution of BzMI-VT-HEMA-GMA copolymer) After adding 172.0 parts of propylene glycol monomethyl ether acetate to the reaction tank provided with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port and nitrogen-substituting, it heated up to 90 degreeC. On the other hand, 10.0 parts of N-benzylmaleimide, 43.6 parts of vinyltoluene, 30.0 parts of 2-hydroxyethyl methacrylate, methyl methacrylate were prepared in a beaker serving as a dropping tank (A). 16.4 parts of glycidyl acrylate, 30 parts of propylene glycol monomethyl ether acetate, and 2.0 parts of 3-butyl peroxy 2-ethylhexanoate ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) were stirred and mixed A product prepared by stirring and mixing 2.0 parts of n-dodecyl mercaptan and 31.33 parts of propylene glycol monomethyl ether acetate in a dropping tank (B). After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 11.5 parts of succinic anhydrides, 0.33 parts of triethylamine as a catalyst, and 29.0 parts of propylene glycol monomethyl ether acetate were reacted at 60° C. for 10 hours to obtain a copolymer solution A-3. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 4) Preparation of copolymer solution A-4 (SAH adduct solution of BzMI-2EHA-HEMA-GMA copolymer) After adding 172.0 parts of propylene glycol monomethyl ether acetate to the reaction tank provided with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port and nitrogen-substituting, it heated up to 90 degreeC. On the other hand, 10.0 parts of N-benzylmaleimide, 43.6 parts of 2-ethylhexyl acrylate, and 30.0 parts of 2-hydroxyethyl methacrylate were prepared in a beaker serving as a dropping tank (A). parts, 16.4 parts of glycidyl methacrylate, 30 parts of propylene glycol monomethyl ether acetate, 3-butyl peroxide 2-ethylhexanoate ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) 2.0 2.0 parts of n-dodecyl mercaptan and 31.33 parts of propylene glycol monomethyl ether acetate were prepared by stirring and mixing in the dropping tank (B). After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 11.5 parts of succinic anhydrides, 0.33 parts of triethylamine as a catalyst, and 29.0 parts of propylene glycol monomethyl ether acetate were reacted at 60° C. for 10 hours to obtain a copolymer solution A-4. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 5) Preparation of copolymer solution A-5 (SAH adduct solution of BzMI-CHMA-HEAA-GMA copolymer) After adding 85.6 parts of diethylene glycol ethyl methyl ether to the reaction tank provided with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port, and nitrogen substitution, it heated up to 90 degreeC. On the other hand, 10.0 parts of N-benzylmaleimide, 46.65 parts of cyclohexyl methacrylate, and 26.8 parts of N-hydroxyethyl acrylamide were prepared in a beaker serving as a dropping tank (A). , 16.55 parts of glycidyl methacrylate, 49.8 parts of diethylene glycol ethyl methyl ether, 3-butyl peroxide 2-ethylhexanoate ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) 2.0 2.0 parts of n-dodecyl mercaptan and 98.0 parts of diethylene glycol ethyl methyl ether were prepared by stirring and mixing in the dropping tank (B). After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 13.0 parts of succinic anhydrides and 32.5 parts of diethylene glycol ethyl methyl ether were made to react at 60 degreeC for 10 hours, and the copolymer solution A-5 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 6) Preparation of copolymer solution A-6 (SAH adduct solution of BzMI-CHMA-GLMA-GMA copolymer) After adding 50.1 parts of propylene glycol monomethyl ether acetate and 50.1 parts of diethylene glycol ethyl methyl ether to a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and an introduction port of a dropping tank, and substituted with nitrogen, then heated The temperature was raised to 90°C. On the other hand, 10.0 parts of N-benzylmaleimide, 46.65 parts of cyclohexyl methacrylate, glycerol monomethacrylate (NOF Corporation) were prepared in a beaker serving as a dropping tank (A). "Blemmer GL") 30.0 parts, glycidyl methacrylate 13.35 parts, propylene glycol monomethyl ether acetate 24.1 parts, diethylene glycol ethyl methyl ether 24.1 parts, 2-ethylhexanoic acid peroxide Tributyl ester ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) 2.0 parts is prepared by stirring and mixing 2.0 parts of n-dodecyl mercaptan, propylene glycol monomethyl in the dripping tank (B). 42.5 parts of ether acetate and 42.5 parts of diethylene glycol ethyl methyl ether were stirred and mixed. After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 9.4 parts of succinic anhydride, 12.0 parts of propylene glycol monomethyl ether acetate, and 12.0 parts of diethylene glycol ethyl methyl ether were reacted at 60° C. for 10 hours to obtain a copolymer solution A-6. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 7) Preparation of copolymer solution A-7 (SAH adduct solution of BzMI-CHMA-HEMA-GMA-NIPAM copolymer) After adding 30.9 parts of propylene glycol monomethyl ether acetate to the reaction tank provided with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and an introduction port of a dripping tank, and nitrogen-substituted, it heated up to 90 degreeC. On the other hand, 10.0 parts of N-benzylmaleimide, 23.6 parts of cyclohexyl methacrylate, and 30.0 parts of 2-hydroxyethyl methacrylate were prepared in a beaker serving as a dropping tank (A). , 16.4 parts of glycidyl methacrylate, 20.0 parts of N-isopropyl acrylamide, 10.0 parts of propylene glycol monomethyl ether acetate, 3-butyl peroxide 2-ethylhexanoate (manufactured by NOF Corporation "PERBUTYL (registered trademark) O") 2.0 parts are prepared by stirring and mixing, in the dropping tank (B), 4.0 parts of n-dodecyl mercaptan and 67.4 parts of propylene glycol monomethyl ether acetate are prepared to be stirred and mixed become. After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 11.5 parts of succinic anhydrides and 4.7 parts of propylene glycol monomethyl ether acetate were reacted at 60° C. for 10 hours to obtain a copolymer solution A-7. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 8) Preparation of copolymer solution A-8 (SAH adduct solution of MAA adduct of BzMI-CHMA-HEMA-GMA copolymer) After adding 64.0 parts of propylene glycol monomethyl ether acetate to the reaction tank provided with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port, and nitrogen-substituting, it heated up to 90 degreeC. On the other hand, 10.0 parts of N-benzylmaleimide, 19.0 parts of cyclohexyl methacrylate, and 30.0 parts of 2-hydroxyethyl methacrylate were prepared in a beaker serving as a dropping tank (A). , 41.0 parts of glycidyl methacrylate, 10.0 parts of propylene glycol monomethyl ether acetate, 2.0 parts of 3-butyl peroxide 2-ethylhexanoate ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) What was stirred and mixed was prepared by stirring and mixing 4.0 parts of n-dodecyl mercaptan and 54.82 parts of propylene glycol monomethyl ether acetate in the dropping tank (B). After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 13.5 parts of methacrylic acids, 0.34 parts of triphenylphosphine as a catalyst, and 0.17 parts of Antage W-400 were reacted at 85° C. for 12 hours. Then, after cooling to room temperature, 13.1 parts of succinic anhydrides were made to react at 60 degreeC for 5 hours, and the copolymer solution A-8 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 9) Preparation of copolymer solution A-9 (SAH adduct solution of Karenz MOI adduct of BzMI-CHMA-HEMA-GMA copolymer) After adding 208.7 parts of propylene glycol monomethyl ether acetate to the reaction tank provided with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port and nitrogen-substituting, it heated up to 90 degreeC. On the other hand, 10.0 parts of N-benzylmaleimide, 14.3 parts of cyclohexyl methacrylate, and 55.0 parts of 2-hydroxyethyl methacrylate were prepared in a beaker serving as a dropping tank (A). , 20.7 parts of glycidyl methacrylate, 10.0 parts of propylene glycol monomethyl ether acetate, 2.0 parts of 3-butyl peroxide 2-ethylhexanoate ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) What was stirred and mixed was prepared by stirring and mixing 2.0 parts of n-dodecyl mercaptan and 98.00 parts of propylene glycol monomethyl ether acetate in the dropping tank (B). After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 26.2 parts of 2-isocyanatoethyl methacrylate ("Karenz MOI (registered trademark)" manufactured by Showa Denko), 0.13 parts of triethylamine, and 0.19 parts of Antage W -400 was reacted at 90°C for 4 hours. Then, after cooling to room temperature, 14.7 parts of succinic anhydride and 0.28 parts of triethylamine as a catalyst were reacted at 60° C. for 7 hours, and 69 parts of propylene glycol monomethyl ether were further added and allowed to react at 60° C. for 1 hour, Thereby, the residual succinic anhydride was eliminated, and the copolymer solution A-9 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 10) Preparation of copolymer solution A-10 (SAH adduct solution of AMA-TBMA-HEMA-GMA copolymer) After adding 172 parts of propylene glycol monomethyl ether acetate to the reaction tank provided with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port, and nitrogen-substituting, it heated up to 90 degreeC. On the other hand, 10.0 parts of methyl α-(allyloxymeth)acrylates, 43.6 parts of tertiary butyl methacrylates, and 2-hydroxyethyl methacrylate were prepared in a beaker serving as a dropping tank (A). 30.0 parts of esters, 16.4 parts of glycidyl methacrylate, 30.0 parts of propylene glycol monomethyl ether acetate, 3-butyl peroxide 2-ethylhexanoate ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) ) 2.0 parts were stirred and mixed, and 2.0 parts of n-dodecyl mercaptan and 31.3 parts of propylene glycol monomethyl ether acetate were prepared by stirring and mixing in the dropping tank (B). After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 11.5 parts of succinic anhydrides, 0.33 parts of triethylamine as a catalyst, and 29.04 parts of propylene glycol monomethyl ether acetate were reacted at 60° C. for 10 hours to obtain a copolymer solution A-10. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 11) Preparation of copolymer solution A-11 (SAH adduct solution of AA adduct of MD-CHMA-HEMA-GMA copolymer) After adding 86.5 parts of propylene glycol monomethyl ether acetate to the reaction tank provided with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port, and nitrogen-substituted, it heated up to 90 degreeC. On the other hand, 10.0 parts of dimethyl 2,2'-[oxybis(methylene)]bis-2-acrylate and 43.6 parts of cyclohexyl methacrylate were prepared in a beaker serving as a dropping tank (A). , 30.0 parts of 2-hydroxyethyl methacrylate, 16.4 parts of glycidyl methacrylate, 48.8 parts of propylene glycol monomethyl ether acetate, 3-butyl peroxide 2-ethylhexanoate (manufactured by NOF Corporation "PERBUTYL (registered trademark) O") 2.0 parts are prepared by stirring and mixing, in the dropping tank (B), 2.0 parts of n-dodecyl mercaptan and 98 parts of propylene glycol monomethyl ether acetate are prepared to be stirred and mixed become. After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 5.0 parts of acrylic acid, 0.32 parts of triethylamine as a catalyst, 0.16 parts of Antage W-400, and 20 parts of propylene glycol monomethyl ether acetate were reacted at 115°C for 7 hours. Then, after cooling to room temperature, 12.6 parts of succinic anhydrides and 20 parts of propylene glycol monomethyl ether acetate were reacted at 60° C. for 10 hours to obtain a copolymer solution A-11. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 12) Preparation of copolymer solution A-12 (SAH adduct solution of CHMI-CHMA-HEMA-GMA copolymer) After adding 172 parts of propylene glycol monomethyl ether acetate to the reaction tank provided with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port, and nitrogen-substituting, it heated up to 90 degreeC. On the other hand, 10.0 parts of N-cyclohexylmaleimide, 43.6 parts of cyclohexyl methacrylate, and 30.0 parts of 2-hydroxyethyl methacrylate were prepared in a beaker serving as a dropping tank (A). , 16.4 parts of glycidyl methacrylate, 30.0 parts of propylene glycol monomethyl ether acetate, 2.0 parts of 3-butyl peroxide 2-ethylhexanoate ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) What was stirred and mixed was prepared by stirring and mixing 2.0 parts of n-dodecyl mercaptan and 31.3 parts of propylene glycol monomethyl ether acetate in the dropping tank (B). After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 11.5 parts of succinic anhydrides, 0.33 parts of triethylamine as a catalyst, and 29.0 parts of propylene glycol monomethyl ether acetate were reacted at 60° C. for 10 hours to obtain a copolymer solution A-12. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 13) Preparation of copolymer solution A-13 (SAH adduct solution of BzMI-DCPMA-HEMA-GMA copolymer) After adding 53.4 parts of propylene glycol monomethyl ether acetate to the reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port, it heated up to 90 degreeC after nitrogen substitution. On the other hand, 5.0 parts of N-benzylmaleimide, 25.0 parts of dicyclopentyl methacrylate, and 40.0 parts of 2-hydroxyethyl methacrylate were prepared in a beaker serving as a dropping tank (A). parts, 30.0 parts of glycidyl methacrylate, 10 parts of propylene glycol monomethyl ether acetate, 3-butyl peroxide 2-ethylhexanoate ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) 2.0 6.0 parts of n-dodecyl mercaptan and 54.0 parts of propylene glycol monomethyl ether acetate were prepared by stirring and mixing in the dropping tank (B). After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, after making 23.1 parts of succinic anhydrides and 9.13 parts of propylene glycol monomethyl ether acetates react at 60 degreeC for 12 hours, it diluted with 172 parts of propylene glycol monomethyl ethers. A copolymer solution A-13 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 14) Preparation of copolymer solution A-14 (SAH adduct solution of BzMI-CHMA-HEMA-GMA copolymer) After adding 165.3 parts of propylene glycol monomethyl ether acetate to the reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port, it heated and heated up to 90 degreeC after nitrogen substitution. On the other hand, 10.0 parts of N-benzylmaleimide, 27.5 parts of cyclohexyl methacrylate, and 30.0 parts of 2-hydroxyethyl methacrylate were prepared in a beaker serving as a dropping tank (A). , 32.5 parts of glycidyl methacrylate, 30 parts of propylene glycol monomethyl ether acetate, 2.0 parts of 3-butyl peroxide 2-ethylhexanoate ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) What was stirred and mixed was prepared by stirring and mixing 2.0 parts of n-dodecyl mercaptan and 38.0 parts of propylene glycol monomethyl ether acetate in the dropping tank (B). After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 11.5 parts of succinic anhydride, 0.33 parts of triethylamine as a catalyst, and 29.0 parts of propylene glycol monomethyl ether acetate were reacted at 60° C. for 10 hours, and then reacted with 76 parts of propylene glycol monomethyl ether. dilution. A copolymer solution A-14 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 15) Preparation of copolymer solution A-15 (SAH adduct solution of BzMI-2EHA-HEMA-GMA copolymer) After adding 172.0 parts of propylene glycol monomethyl ether acetate to the reaction tank provided with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port and nitrogen-substituting, it heated up to 90 degreeC. On the other hand, 10.0 parts of N-benzylmaleimide, 29.0 parts of 2-ethylhexyl acrylate, and 30.0 parts of 2-hydroxyethyl methacrylate were prepared in a beaker serving as a dropping tank (A). parts, 31.0 parts of glycidyl methacrylate, 30 parts of propylene glycol monomethyl ether acetate, 3-butyl peroxide 2-ethylhexanoate ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) 2.0 2.0 parts of n-dodecyl mercaptan and 31.33 parts of propylene glycol monomethyl ether acetate were prepared by stirring and mixing in the dropping tank (B). After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 6.2 parts of succinic anhydride, 0.33 parts of triethylamine as a catalyst, and 16.5 parts of propylene glycol monomethyl ether acetate were reacted at 60° C. for 10 hours, and then reacted with 40 parts of propylene glycol monomethyl ether. Diluted to obtain copolymer solution A-15. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 16) Preparation of copolymer solution A-16 (SAH adduct solution of BzMI-CHMA-HEMA-GMA copolymer) After adding 83.6 parts of propylene glycol monomethyl ether acetate to the reaction tank provided with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port, it heated up to 90 degreeC after nitrogen substitution. On the other hand, 20.0 parts of N-benzylmaleimide, 25.0 parts of cyclohexyl methacrylate, and 50.0 parts of 2-hydroxyethyl methacrylate were prepared in a beaker serving as a dropping tank (A). , 5.0 parts of glycidyl methacrylate, 50 parts of propylene glycol monomethyl ether acetate, 2.0 parts of 3-butyl peroxide 2-ethylhexanoate ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) What was stirred and mixed was prepared by stirring and mixing 0.3 parts of n-dodecyl mercaptan and 99.70 parts of propylene glycol monomethyl ether acetate in the dropping tank (B). After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 34.6 parts of succinic anhydrides, 0.40 parts of triethylamine as a catalyst, and 78.9 parts of propylene glycol monomethyl ether acetate were reacted at 60° C. for 10 hours to obtain a copolymer solution A-16. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 17) Preparation of copolymer solution A-17 (SAH adduct solution of AA adduct of BzMI-CHMA-HEMA-GMA copolymer) After adding 16.6 parts of propylene glycol monomethyl ether acetate to the reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port, and nitrogen-substituting, it heated up to 90 degreeC. On the other hand, 30.0 parts of N-benzylmaleimide, 10.0 parts of cyclohexyl methacrylate, and 10.0 parts of 2-hydroxyethyl methacrylate were prepared in a beaker serving as a dropping tank (A). , 50.0 parts of glycidyl methacrylate, 30.0 parts of propylene glycol monomethyl ether acetate, 2.0 parts of 3-butyl peroxide 2-ethylhexanoate ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) What was stirred and mixed was prepared by stirring and mixing 6.0 parts of n-dodecyl mercaptan and 82.24 parts of propylene glycol monomethyl ether acetate in the dropping tank (B). After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 22.8 parts of acrylic acids, 0.37 parts of triphenylphosphine as a catalyst, and 0.18 parts of Antage W-400 were reacted at 85°C for 12 hours. Then, after cooling to room temperature, after making 4.6 parts of succinic anhydrides react at 60 degreeC for 8 hours, it diluted with 118 parts of propylene glycol monomethyl ether, and obtained the copolymer solution A-17. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 18) Preparation of copolymer solution A-18 (SAH adduct solution of Karenz MOI adduct of BzMI-CHMA-HEMA-GMA copolymer) After adding 78.6 parts of propylene glycol monomethyl ether acetate to the reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port, it heated up to 90 degreeC after nitrogen substitution. On the other hand, 10.0 parts of N-benzylmaleimide, 29.3 parts of cyclohexyl methacrylate, and 40.0 parts of 2-hydroxyethyl methacrylate were prepared in a beaker serving as a dropping tank (A). , 20.7 parts of glycidyl methacrylate, 10.0 parts of propylene glycol monomethyl ether acetate, 6.0 parts of 3-butyl peroxide 2-ethylhexanoate ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) What was stirred and mixed was prepared by stirring and mixing 2.0 parts of n-dodecyl mercaptan and 48.00 parts of propylene glycol monomethyl ether acetate in the dropping tank (B). After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 4.8 parts of 2-isocyanatoethyl methacrylate (“Karenz MOI (registered trademark)” manufactured by Showa Denko) and 0.16 parts of Antage W-400 were reacted at 90° C. 8 Hour. Then, after cooling to room temperature, 14.6 parts of succinic anhydrides and 0.36 parts of triethylamine as a catalyst were reacted at 60° C. for 10 hours to obtain a copolymer solution A-18. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 19) Preparation of Copolymer Solution B-1 (BzMI-CHMA-HEMA-Cyclomer M100-MAA Copolymer) After adding 145.3 parts of propylene glycol monomethyl ether acetate to the reaction tank provided with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port and nitrogen-substituting, it heated up to 90 degreeC. On the other hand, 10.0 parts of N-benzylmaleimide, 47.4 parts of cyclohexyl methacrylate, and 13.45 parts of 2-hydroxyethyl methacrylate were prepared in a beaker serving as a dropping tank (A). , 3,4-epoxycyclohexyl methyl methacrylate (“Cyclomer M100 (registered trademark)” manufactured by Daicel) 20.25 parts, 8.9 parts of methacrylic acid, 10.0 parts of propylene glycol monomethyl ether acetate, trimethyl peroxide 2.7 parts of tert-butyl glycolate ("Luperox 11 (registered trademark)" manufactured by Arkema Yoshitomi Co., Ltd.) was stirred and mixed, and 2.0 parts of n-dodecyl mercaptan, 2.0 parts of n-dodecyl mercaptan, 78 parts of propylene glycol monomethyl ether acetate were stirred and mixed. After the temperature of the reaction tank became 70° C., while maintaining the temperature, it started dripping from the dripping tank over 3 hours to perform polymerization. After completion of the dropwise addition, the mixture was kept at 70° C. for 30 minutes, then the temperature was raised to 80° C., and aging was performed for 180 minutes to obtain a copolymer solution B-1. Various physical properties of the obtained copolymer are shown in Table 1.

(Manufacturing Example 20) Preparation of Copolymer Solution B-2 (BzMI-CHMA-HEMA-GMA-MAA Copolymer) After adding 145.3 parts of propylene glycol monomethyl ether acetate to the reaction tank provided with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port, and nitrogen-substituting, it heated up to 70 degreeC. On the other hand, 10.0 parts of N-benzylmaleimide, 52.95 parts of cyclohexyl methacrylate, and 13.45 parts of 2-hydroxyethyl methacrylate were prepared in a beaker serving as a dropping tank (A). , 14.7 parts of glycidyl methacrylate, 8.9 parts of methacrylic acid, 10.0 parts of propylene glycol monomethyl ether acetate, tert-butyl peroxytrimethyl acetate ("Luperox 11 (registered trademark)" manufactured by Arkema Yoshitomi Co., Ltd. ”) 2.7 parts were stirred and mixed, and 2.0 parts of n-dodecyl mercaptan and 78 parts of propylene glycol monomethyl ether acetate were prepared by stirring and mixing in the dropping tank (B). After the temperature of the reaction tank became 70° C., while maintaining the temperature, it started dripping from the dripping tank over 3 hours to perform polymerization. After completion of the dropwise addition, the mixture was kept at 70°C for 30 minutes, then the temperature was raised to 80°C, and aging was performed for 180 minutes to obtain a copolymer solution B-2. Various physical properties of the obtained copolymer are shown in Table 1.

[Table 1] Example Comparative example Copolymer No. A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 A-13 A-14 A-15 A-16 A-17 A-18 B-1 B-2 Co-monomer (parts) BzMI - 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 - - - 5.0 10.0 10.0 20.0 30.0 10.0 10.0 10.0 AMA - - - - - - - - - 10.0 - - - - - - - - - - MD - - - - - - - - - - 10.0 - - - - - - - - - CHMI - - - - - - - - - - - 10.0 - - - - - - - - CHMA - 43.6 - - 46.65 46.65 23.6 19.0 14.3 - 43.6 43.6 - 27.5 - 25.0 10.0 29.3 47.4 52.95 VT - - 43.6 - - - - - - - - - - - - - - - - - 2EHA - - - 43.6 - - - - - - - - - - 29.0 - - - - - DCPMA - - - - - - - - - - - - 25.0 - - - - - - - TBMA - - - - - - - - - 43.6 - - - - - - - - - - HEMA 30.0 30.0 30.0 30.0 - - 30.0 30.0 55.0 30.0 30.0 30.0 40.0 30.0 30.0 50.0 10.0 40.0 13.45 13.45 HEAA - - - - 26.8 - - - - - - - - - - - - - - - GLMA - - - - - 30.0 - - - - - - - - - - - - - - M100 - - - - - - - - - - - - - - - - - - 20.25 - GMA 70.0 16.4 16.4 16.4 16.55 13.35 16.4 41.0 20.7 16.4 16.4 16.4 30.0 32.5 31.0 5.0 50.0 20.7 - 14.7 NIPAM - - - - - - 20.0 - - - - - - - - - - - - - MAA - - - - - - - - - - - - - - - - - - 8.9 8.9 Addition (parts) AA - - - - - - - - - - 5.0 - - - - - 22.8 - - - MAA - - - - - - - 13.5 - - - - - - - - - - - - Karenz MOI - - - - - - - - 26.2 - - - - - - - - 4.8 - - SAH 11.5 11.5 11.5 11.5 13.0 9.4 11.5 13.1 14.7 11.5 12.6 11.5 23.1 11.5 6.2 34.6 4.6 14.6 - - Mw 15900 15400 15500 15200 14500 14800 13100 10200 18200 14000 15400 15000 5000 15600 14000 25000 12000 17000 14000 14500 Acid value (mgKOH/g) 67 61 59 57 64 54 61 64 64 58 61 60 105 57 33 149 20 73 58 56 Epoxy equivalent (g/equivalent) 231 985 985 985 988 1186 1002 997 985 985 2610 985 612 497 496 3836 3810 837 969 967 Double bond equivalent (g/equivalent) - - - - - - - 836 849 - 1730 - - - - - 423 3966 - -

In addition, the description in Table 1 is as follows. BzMI: N-benzylmaleimide AMA: Methyl α-(allyloxymethyl)acrylate MD: Dimethyl 2,2'-[oxybis(methylene)]bis-2-acrylate CHMI: N-Cyclohexylmaleimide CHMA: cyclohexyl methacrylate VT: Vinyl Toluene 2EHA: 2-ethylhexyl acrylate DCPMA: Dicyclopentyl methacrylate TBMA: tert-butyl methacrylate HEMA: 2-hydroxyethyl methacrylate HEAA: N-Hydroxyethyl acrylamide GLMA: Glycerol Monomethacrylate M100: 3,4-epoxycyclohexylmethyl methacrylate GMA: Glycidyl methacrylate NIPAM: N-Isopropylacrylamide MAA: methacrylic acid AA: Acrylic Karenz MOI: 2-Methacryloyloxyethyl isocyanate SAH: Succinic Anhydride

(Preparation of Pigment Dispersion 1) Mix 12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparlon DA-7301 as a dispersant, 2.25 parts of C.I. Pigment Green 58 as a colorant, and 1.5 parts of C.I. Pigment Yellow 138, and use a paint shaker (paint Shaker) was dispersed for 3 hours to obtain Pigment Dispersion 1 (solid content 22 mass %).

(Example 1) In terms of solid content, 35.0 parts of the copolymer solution A-1, 30.0 parts of dinepentaerythritol hexaacrylate as a radically polymerizable compound, and Irgacure OXE-02 (as a radically polymerizable photopolymerization initiator) were added. BASF JAPAN Co., Ltd.) 5.0 parts, 1 30.0 parts of pigment dispersion, further adding a diluting solvent (propylene glycol monomethyl ether acetate) so that the solid content concentration becomes 20%, and stirring, to obtain a photosensitive resin composition 1.

(Examples 2 to 18, Comparative Examples 1 to 2) Except having set it as the composition shown in Table 2, it carried out similarly to Example 1, and obtained the photosensitive resin composition 2-20. The solvent resistance of the obtained photosensitive resin compositions 1-20 was evaluated. The results are shown in Table 2.

[Table 2] Example Comparative example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 1 2 Curable resin composition No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Composition (parts) A-1 35.0 - - - - - - - - - - - - - - - - - - - A-2 - 35.0 - - - - - - - - - - - - - - - - - - A-3 - - 35.0 - - - - - - - - - - - - - - - - - A-4 - - - 35.0 - - - - - - - - - - - - - - - - A-5 - - - - 35.0 - - - - - - - - - - - - - - - A-6 - - - - - 35.0 - - - - - - - - - - - - - - A-7 - - - - - - 35.0 - - - - - - - - - - - - - A-8 - - - - - - - 35.0 - - - - - - - - - - - - A-9 - - - - - - - - 35.0 - - - - - - - - - - - A-10 - - - - - - - - - 35.0 - - - - - - - - - - A-11 - - - - - - - - - - 35.0 - - - - - - - - - A-12 - - - - - - - - - - - 35.0 - - - - - - - - A-13 - - - - - - - - - - - - 35.0 - - - - - - - A-14 - - - - - - - - - - - - - 35.0 - - - - - - A-15 - - - - - - - - - - - - - - 35.0 - - - - - A-16 - - - - - - - - - - - - - - - 35.0 - - - - A-17 - - - - - - - - - - - - - - - - 35.0 - - - A-18 - - - - - - - - - - - - - - - - - 35.0 - - B-1 - - - - - - - - - - - - - - - - - - 35.0 - B-2 - - - - - - - - - - - - - - - - - - - 35.0 polymeric compound Dipivalerythritol hexaacrylate 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 photopolymerization initiator Irgacure OXE-02 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Pigment Dispersion 1 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 solvent Propylene Glycol Monomethyl Ether Acetate The solid content concentration is 20% by mass Evaluation 90℃PoB Solvent Resistance-Absorbance[/2 μm] ○ ○ ○ ○ ○ ○ ○ ◎ ◎ ○ ○ ○ ○ ○ ○ × △ ○ ×× ×× 110℃CPoB Solvent Resistance-Absorbance[/2 μm] ◎ ○ ○ ◎ ○ ○ ◎ ◎ ◎ ○ ◎ ○ ◎ ◎ ○ △ ○ ○ ×× ××

According to Table 2, the photosensitive resin composition containing a copolymer having an epoxy-group-containing structural unit and a long-chain acid-group-containing structural unit and an epoxy equivalent of 20,000 or less even at a low temperature of 90°C or 110°C Under the curing conditions, a cured product with good curability and excellent solvent resistance can also be formed.

Example 19, Comparative Example 3 (Confirmation of storage stability) In order to study the effect of the storage stability by the dilution solvent, the following operation was performed. Using a copolymer solution in which 20 parts (equivalent to 66.7 mass % of the solid content of the copolymer) was added to 100 parts (wet weight) of the copolymer solution A-2, it was confirmed that it was stored at 40° C. for 2 Changes in physical properties (weight average molecular weight and viscosity) of the copolymer before and after the week. As the dilution solvent, two types of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether were used. Table 3 shows changes in physical properties of the obtained copolymer solutions. Regarding the weight average molecular weight, the ratio (%) of the difference between the weight average molecular weights before and after storage with respect to the weight average molecular weight before storage is shown as the amount of change. About the viscosity, the ratio (%) of the difference of the viscosity before and after storage with respect to the viscosity before storage is shown.

[table 3] Example 19 Comparative Example 3 Copolymer A-2 100 copies 100 copies Dilution solvent (mass % relative to 100 mass % of copolymer solid content) Propylene Glycol Monomethyl Ether 20 (66.7%) - Propylene Glycol Monomethyl Ether Acetate - 20 (66.7%) Store at 40°C for 2 weeks Variation Physical property changes Mw (%) 2 14 Viscosity (%) 105 176

According to Table 3, when propylene glycol monomethyl ether as an alcohol-based solvent was added, compared with the case where propylene glycol monomethyl ether acetate was added, the change in weight average molecular weight and the change in viscosity after storage When the amount is small, the storage stability of the copolymer is excellent.

(Manufacturing Example 21) Preparation of Copolymer Solution A-19 After adding 105.3 parts of propylene glycol monomethyl ether acetate to the reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a condenser pipe, and a drip tank introduction port, and nitrogen-substituting, it heated up to 90 degreeC. On the other hand, 10.0 parts of N-benzylmaleimide, 27.5 parts of cyclohexyl methacrylate, and 30.0 parts of 2-hydroxyethyl methacrylate were prepared in a beaker serving as a dropping tank (A). , 32.5 parts of glycidyl methacrylate, 30 parts of propylene glycol monomethyl ether acetate, 2.0 parts of 3-butyl peroxide 2-ethylhexanoate ("PERBUTYL (registered trademark) O" manufactured by NOF Corporation) What was stirred and mixed was prepared by stirring and mixing 2.0 parts of n-dodecyl mercaptan and 98.0 parts of propylene glycol monomethyl ether acetate in the dropping tank (B). After the temperature of the reaction tank became 90° C., the temperature was maintained, and the polymerization was started by dripping from the dropping tank over 3 hours. After completion of the dropwise addition, the temperature was raised to 115° C. after holding at 90° C. for 30 minutes, and aging was performed for 90 minutes. Then, after cooling to room temperature, 11.5 parts of succinic anhydrides, 0.33 parts of triethylamine as a catalyst, and 29.0 parts of propylene glycol monomethyl ether acetate were added and reacted at 60°C for 7 hours. Then, 42.0 parts of propylene glycol monomethyl ethers were added so that solid content might become 27%, and the copolymer solution A-19 was obtained. Various physical properties of the obtained copolymers are shown in Table 4.

(Manufacturing Example 22) Preparation of Copolymer Solution A-20 A copolymer solution A-20 was obtained by the same preparation method as that of the copolymer solution A-19, except that propylene glycol monomethyl ether acetate was added instead of propylene glycol monomethyl ether. Various physical properties of the obtained copolymers are shown in Table 4.

[Table 4] Copolymer No. A-19 A-20 Co-monomer (parts) BzMI 10.0 10.0 CHMA 27.5 27.5 HEMA 30.0 30.0 GMA 32.5 32.5 Addition monomer (parts) SAH 11.5 11.5 Addition catalyst (parts) TEA 0.33 0.33 synthetic solvent Propylene Glycol Monomethyl Ether Acetate Dilution solvent (diluted to a solid content of 27%) Propylene Glycol Monomethyl Ether Propylene Glycol Monomethyl Ether Acetate Mw 15600 15600 Acid value (mgKOH/g) 57 57 Epoxy equivalent (g/equivalent) 496 496

In addition, the description in Table 4 is as follows. BzMI: N-benzylmaleimide CHMA: cyclohexyl methacrylate HEMA: 2-hydroxyethyl methacrylate GMA: Glycidyl methacrylate SAH: Succinic Anhydride TEA: Triethylamine

(Example 20) In terms of solid content, 35.0 parts of the copolymer solution A-19, 30.0 parts of dinepentaerythritol hexaacrylate as a radically polymerizable compound, and Irgacure OXE-02 (as a radically polymerizable photopolymerization initiator) were added. BASF JAPAN Co., Ltd.) 5.0 parts, Pigment Dispersion 1 30.0 parts, P-2M (LIGHT ESTER P-2M, pKa: 1.29, manufactured by Kyōeisha Chemical Co., Ltd.) 1.0 parts, and added so that the solid content concentration would be 20% The photosensitive resin composition 21 was obtained by diluting the solvent (propylene glycol monomethyl ether acetate) and stirring.

(Examples 21 to 23) Except having made the composition shown in Table 5, it carried out similarly to Example 20, and obtained the photosensitive resin composition 22-24. The solvent resistance of the obtained photosensitive resin compositions 21-24 was evaluated. The results are shown in Table 5.

[table 5] Example 20 Example 21 Example 22 Example 23 Photosensitive resin composition No. twenty one twenty two twenty three twenty four Composition (parts) Copolymer A-19 35.0 35.0 35.0 35.0 polymeric compound Dipivalerythritol hexaacrylate 30.0 30.0 30.0 30.0 photopolymerization initiator Irgacure OXE-02 5.0 5.0 5.0 5.0 Pigment Dispersion 1 30.0 30.0 30.0 30.0 additive P-2M 1.0 1.0 - - solvent Propylene Glycol Monomethyl Ether Acetate The solid content concentration is 20% by mass Evaluation Impregnation solvent Propylene Glycol Monomethyl Ether Acetate Propylene Glycol Monomethyl Ether Propylene Glycol Monomethyl Ether Acetate Propylene Glycol Monomethyl Ether Residual film rate (%) 93 86 93 84 90℃PoB Solvent Resistance-Absorbance[/2 μm] 0.09 0.13 0.06 0.23

According to Table 5, the photosensitive resin composition containing a copolymer having an epoxy group-containing structural unit and an acid group-containing structural unit and an epoxy equivalent of 20,000 or less has a high curability even under a low temperature curing condition of 90°C. Also good and excellent in solvent resistance.

Examples 24 to 40 (Confirmation of storage stability) A diluent solvent (propylene glycol monomethyl ether) and P-1M, P-2M, MSA or ACA were added to 100 parts (wet weight) of the copolymer solution in the amounts described in Table 6 or Table 7 to prepare a copolymer solution. The amount of the dilution solvent in Table 6 (35 parts) corresponds to 129.6 mass % relative to 100 mass % of the copolymer solid content, and in Table 7 (8 parts), relative to 100 mass % of the copolymer solid content, It is equivalent to 29.6 mass %. Using the obtained copolymer solution, changes in physical properties (viscosity) of the copolymer solution before and after storage at 40° C. for 1 to 2 weeks were confirmed. Changes in the physical properties of the obtained copolymer solutions are shown in Tables 6 and 7. The ratio (%) of the difference between the viscosity before and after storage with respect to the viscosity before storage was shown as the amount of change in viscosity (viscosity increase rate). In addition, the content of the acid compound (P-1M, P-2M, MSA, ACA) in the copolymer solution with respect to 100 mol% of the basic compound (TEA) is shown in the table.

[Table 6] Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Composition (parts) Copolymer solution A-19 100 100 100 100 - - - - Copolymer solution A-20 - - - - 100 100 100 100 P-2M - 1 0.5 - - 1 0.5 - P-1M - - - 1 - - - 1 Propylene Glycol Monomethyl Ether 35 35 35 35 35 35 35 35 Content of acid compound relative to 100 mol % of basic compound (mol %) 0 105 52 161 0 105 52 161 Blend solid content (%) 20 Initial viscosity [mPa s] 11 11 11 11 12 12 12 12 Viscosity (40℃, 2 weeks) [mPa s] 170 16 26 16 430 twenty one 53 twenty one Viscosity increase rate [%] 1566 140 229 141 3469 167 430 171

[Table 7] Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 Example 38 Example 39 Example 40 Composition (parts) Copolymer solution A-20 100 100 100 100 100 100 100 100 100 P-2M - 1 1.5 2 - - - - - MSA - - - - 0.25 0.5 - - - ACA - - - - - - 0.25 0.5 1 Propylene Glycol Monomethyl Ether 8 8 8 8 8 8 8 8 8 Content of acid compound relative to 100 mol % of basic compound (mol %) 0 105 157 209 88 175 140 281 562 Blend solid content (%) 25 Initial viscosity [mPa s] 38 38 39 39 38 39 39 39 39 Viscosity (40℃, 1 week) [mPa s] 166 52 98 154 129 69 179 171 181 Viscosity increase rate [%] 433 137 253 392 339 177 459 438 464

In addition, the description in Table 6 and Table 7 is as follows. P-1M: LIGHT ESTER P-1M (manufactured by Kyōeisha Chemical Co., Ltd.) acid 2-methacryloyloxyethyl phosphate, pKa: 1.78, molecular weight: 210.12 P-2M: LIGHT ESTER P-2M (manufactured by Kyoeisha Chemical Co., Ltd.) acid 2-methacryloyloxyethyl phosphate, pKa: 1.29, molecular weight: 322.25 MSA: methanesulfonic acid, pKa: -2.6, molecular weight: 96.1 ACA: acetic acid, pKa: 4.76, molecular weight: 60.05

From Table 6 and Table 7, it was confirmed that in a copolymer solution containing a copolymer having an epoxy group-containing structural unit and an acid group-containing structural unit and an epoxy equivalent of 20,000 or less, and a protic polar solvent, by Furthermore, if an acid compound having a pKa of 4.2 or less is contained, the viscosity increase rate after storage is reduced, and the storage stability is excellent.

none

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Claims (14)

A copolymer, characterized in that it has an epoxy group-containing structural unit (A) represented by the following general formula (1), and an acid group-containing structural unit (B) represented by the following general formula (2) , and the epoxy equivalent is less than 20000,

(In formula (1), R ¹ represents a hydrogen atom or a methyl group; R ² represents a direct bond or a divalent organic group; X represents a group containing an epoxy group)

(In formula (2), R ³ represents a hydrogen atom or a methyl group; R ⁴ represents a direct bond or an organic group; R ⁵ represents a bond chain with a length of 2 atoms or more; Y represents an acid group; a represents 0 or 1 ). The copolymer of claim 1, wherein the structural unit (A) comprises a structural unit represented by the following general formula (1-1),

(In formula (1-1), R ¹ represents a hydrogen atom or a methyl group; R ⁶ represents a direct bond or a divalent organic group). The copolymer of claim 1 or 2, wherein the structural unit (B) comprises a structural unit represented by the following general formula (2-1),

(In formula (2-1), R ³ represents a hydrogen atom or a methyl group; R ⁷ and R ⁸ are the same or different, and represent a direct bond or an organic group; b represents 0 or 1). The copolymer according to any one of claims 1 to 3, which is a copolymer having a ring structure in the main chain. A copolymer solution characterized by containing the copolymer of any one of claims 1 to 4, and a protic polar solvent. The copolymer solution according to claim 5, which further contains an acid compound with a pKa of 4.2 or less. The copolymer solution of claim 5 or 6, which further contains a phosphoric acid derivative. The copolymer solution according to any one of claims 5 to 7, which further contains a basic compound. A photosensitive resin composition comprising the copolymer of any one of claims 1 to 4 or the copolymer solution of any one of claims 5 to 8, a polymerizable compound, and a photopolymerization initiator. The photosensitive resin composition of claim 9 further contains a colorant. The photosensitive resin composition of claim 9 or 10 is for negative type. A hardened product, which is the hardened product of the copolymer of any one of claims 1 to 4, the hardened product of the copolymer solution of any one of claims 5 to 8, or the hardened product of any one of claims 9 to 11 Cured product of photosensitive resin composition. A method for producing a copolymer, comprising: adding a monomer component comprising an epoxy group-containing monomer represented by the following formula (a) and a hydroxyl group-containing monomer represented by the following formula (b1). A step of conducting polymerization; and a step of reacting the polymer obtained in the polymerization step with an acid group-containing compound represented by the following formula (b2) or formula (b3);

(In formula (a), R ¹ represents a hydrogen atom or a methyl group; R ² represents a direct bond or a divalent organic group; X represents a group containing an epoxy group)

(In formula (b1), R ³ represents a hydrogen atom or a methyl group; R ⁴ represents a direct bond or an organic group)

(In formula (b2), R ⁵ represents a bond chain with a length of 2 atoms or more; Y represents an acid group)

(In formula (b3), R ⁵ represents a bond chain having a length of 2 atoms or more). A method for producing a copolymer solution, comprising: mixing a monomer comprising an epoxy group-containing monomer represented by the following formula (a) and a hydroxyl group-containing monomer represented by the following formula (b1) A step of polymerizing the components; a step of reacting the polymer obtained in the polymerization step with an acid group-containing compound represented by the following formula (b2) or formula (b3) in the presence of a basic compound; and adding pKa Steps for acid compounds below 4.2 and protic polar solvents;

(In formula (a), R ¹ represents a hydrogen atom or a methyl group; R ² represents a direct bond or a divalent organic group; X represents a group containing an epoxy group)

(In formula (b1), R ³ represents a hydrogen atom or a methyl group; R ⁴ represents a direct bond or an organic group)

(In formula (b2), R ⁵ represents a bond chain with a length of 2 atoms or more; Y represents an acid group)

(In formula (b3), R ⁵ represents a bond chain having a length of 2 atoms or more).