KR20230015406A - Copolymer, copolymer solution, photosensitive resin composition, cured product, method for producing copolymer, and method for producing copolymer solution - Google Patents

Abstract

(식 (1) 중, R¹ 은, 수소 원자 또는 메틸기를 나타낸다. R² 는, 직접 결합, 또는, 2 가의 유기기를 나타낸다. X 는, 에폭시기 함유기를 나타낸다.)

(식 (2) 중, R³ 은, 수소 원자 또는 메틸기를 나타낸다. R⁴ 는, 직접 결합, 또는, 유기기를 나타낸다. R⁵ 는, 길이가 2 원자 이상인 결합 사슬을 나타낸다. Y 는, 산기를 나타낸다. a 는, 0 또는 1 을 나타낸다.)An object of the present invention is to provide a copolymer that can provide a cured product having excellent solvent resistance even under low-temperature curing conditions and can be suitably used as a thermosetting resin for various applications such as color filters. The present invention is a copolymer 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 having an epoxy equivalent of 20000 or less. am.

(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 an epoxy group-containing 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 bonded chain having a length of 2 atoms or more. Y represents an acid group 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 copolymers. More specifically, it relates to a copolymer capable of providing a cured product having excellent solvent resistance even under low-temperature curing conditions, a copolymer solution, a photosensitive resin composition, a cured product, a method for producing a copolymer, and a method for producing a copolymer solution. will be.

A composition containing a curable resin is, for example, a color filter used for a liquid crystal display device or a solid-state imaging device, an ink, a printed board, a printed wiring board, a semiconductor device, a photoresist, various optical members such as an organic insulating film, an organic protective film, and an electrical · Application to various uses, such as electronic devices, is being studied in various ways, and resins and resin compositions with excellent properties required for each use are being developed.

In recent years, miniaturization, thinning, and energy saving of optical members, electric/electronic devices, and the like are progressing, and with it, higher quality performance is desired for various members and the like to be used. In order to meet such requests, research is being conducted on curable resins used as materials for various members and the like.

Until now, curable resins according to various requirements have been developed.

For example, in Patent Document 1, a photosensitive resin composition containing an oligomer having a carboxyl group and a photoreactive unsaturated group in a side chain and soluble in an aqueous alkali solution, a compound having an epoxy group, a sensitizer, and a dicyandiamide-modified product. are listed.

Further, for example, Patent Document 2 describes a photosensitive composition containing an alkali-soluble polymer obtained by polymerizing a radical polymerizable monomer having an epoxy group or an oxetanyl group, a radical polymerizable monomer having a carboxyl group, or the like.

Further, for example, in Patent Document 3, a (meth)acrylate monomer having a glass transition temperature of 10° C. or less when used as a homopolymer, and an addition copolymer such as a (meth)acrylate monomer having an epoxy group or a carboxyl group, specific A curable polymer having an acid group, a hydroxyl group, and a polymerizable unsaturated bond in a side chain obtained by performing a denaturation reaction, and a photosensitive polymer composition containing the curable polymer are described.

Japanese Unexamined Patent Publication No. 4-25846 Japanese Unexamined Patent Publication No. 2006-251009 Japanese Unexamined Patent Publication No. 2014-210892

As described above, curable resins have been studied variously so far, but when conventional curable resins are used together with color materials as raw materials such as color filters, for example, from raw materials to cleaning solvents during production of color filters. There was a problem that the color material was eluted. Therefore, further improvement in the solvent resistance of curable resins has been required.

In recent years, especially in color filter applications, higher performance, such as higher luminance and higher contrast, of display panels has been strongly demanded due to higher quality of color liquid crystal display devices and the like and expansion of applications. However, in the production of a color filter, when the firing treatment step (post-curing step) after exposure and development is performed at a high temperature of more than 200°C, discoloration such as yellowing occurs in the obtained cured product, and coloration with a desired color is not achieved. There was a problem that it could not be implemented sufficiently. In addition, when the firing treatment step is performed at a high temperature, there is also a problem that unnecessary reactions proceed and by-products are generated, thereby deteriorating the properties of the base material or the cured film. In order to suppress such an unnecessary reaction and efficiently obtain a color filter having desired characteristics, it is preferable that the curing reaction sufficiently proceeds even under relatively low heating conditions of 200°C or less. Moreover, if curable resin composition can be hardened at a comparatively low temperature, the manufacturing efficiency of a color filter can also be improved.

In the conventional photosensitive resin composition described in Patent Literature 1, a high temperature is required in the synthesis of the resin. Further, there is room for improvement in the curability of the resin.

The present invention has been made in view of the above situation, and provides a copolymer that can give a cured product having excellent solvent resistance even under low-temperature curing conditions and can be suitably used as a thermosetting resin for various applications such as color filters. aims to do

As a result of various studies on the curable resin, the present inventors found that 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 was obtained, even under low-temperature curing conditions of 160 ° C. or less. The crosslinking reaction proceeded favorably, and it was discovered that a cured product having excellent solvent resistance could be provided, and the present invention was completed.

That is, 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 having an epoxy equivalent of 20000 or less. It is a copolymer.

[Formula 1]

(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 an epoxy group-containing group.)

[Formula 2]

(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 bonded chain having a length of 2 atoms or more. Y represents an acid group represents 0 or 1.)

In the above copolymer, it is preferable that the structural unit (A) includes a structural unit represented by the following general formula (1-1).

[Formula 3]

(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 copolymer, it is preferable that the structural unit (B) includes a structural unit represented by the following general formula (2-1).

[Formula 4]

(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. )

It is preferable that the said copolymer is a copolymer which further has a cyclic structure in a principal chain.

It is preferable that the said copolymer further contains the structural unit derived from the monomer whose longest side chain has 5-20 atoms or the monomer which has a ring structure in a side chain.

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

It is preferable that the copolymer solution further contains an acid compound having a pKa of 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.

This invention is also the photosensitive resin composition characterized by containing the above-mentioned copolymer or copolymer solution, a polymeric compound, and a photoinitiator.

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

It is preferable that the said photosensitive resin composition is for negative types.

This invention is also a hardened|cured material of the above-mentioned copolymer, the above-mentioned copolymer solution, or the above-mentioned photosensitive resin composition.

The present invention further relates to a step of polymerizing a monomer component containing an epoxy group-containing monomer represented by the following formula (a) and a hydroxyl group-containing monomer represented by the following formula (b1), the polymer obtained in the polymerization step, and the following formula ( It is also a method for producing a copolymer characterized by including a step of reacting the acid group-containing compound represented by b2) or formula (b3).

[Formula 5]

(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 an epoxy group-containing group.)

[Formula 6]

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

[Formula 7]

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

[Formula 8]

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

The present invention further relates to a step of polymerizing a monomer component containing an epoxy group-containing monomer represented by the following formula (a) and a hydroxyl group-containing monomer represented by the following formula (b1), the polymer obtained in the polymerization step, and the following formula ( A copolymer solution characterized by including a step of reacting the acid group-containing compound represented by b2) or formula (b3) in the presence of a basic compound, a step of adding an acid compound having a pKa of 4.2 or less, and a protic polar solvent. It is also a manufacturing method of

[Formula 9]

(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 an epoxy group-containing group.)

[Formula 10]

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

[Formula 11]

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

[Formula 12]

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

The copolymer of the present invention can provide a cured product having excellent solvent resistance even under a relatively low temperature curing condition of 160°C or lower. The copolymer of the present invention is suitable for various applications such as various optical members used for liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state imaging devices, touch panel display devices, etc., and structural members such as electric/electronic devices. preferably used.

The present invention is described in detail below.

In addition, a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present 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 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 has an epoxy equivalent of 20000 or less. do.

[Formula 13]

(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 an epoxy group-containing group.)

[Formula 14]

(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 bonded chain having a length of 2 atoms or more. Y represents an acid group represents 0 or 1.)

The copolymer of the present invention can give a cured product having excellent solvent resistance even under relatively low curing conditions of 160°C or lower (preferably around 90°C), those having an epoxy group and an acid group, and an acid group Since it is a long chain acid located relatively far from the main chain, the acid group reacts very easily with the epoxy group, and the crosslinking reaction proceeds even at a relatively low temperature to form a strong cured film, and the side chain of the structural unit containing the acid group. It is presumed that this is because the glass transition temperature becomes lower than that of the structural units of acrylic acid or methacrylic acid, the polymer side chain becomes more flexible, and the crosslinking reaction proceeds easily at low temperatures.

The copolymer of the present invention has the above epoxy group-containing structural unit (A) and acid group-containing structural unit (B), and the epoxy equivalent (g/equivalent) is 20000 or less. When the epoxy equivalent exceeds 20000, there is a possibility that the curing is insufficient and the solvent resistance is lowered. The epoxy equivalent of the copolymer of the present invention is preferably 10000 or less, more preferably 8000 or less, still more preferably 5000 or less, still more preferably 4000 or less, particularly preferably 3000 or less, and most preferably 2000 or less. Do. Moreover, it is preferable that it is 100 or more, it is more preferable that it is 150 or more, and, as for the said epoxy equivalent, it is more preferable that it is 200 or more from the point of storage stability.

The epoxy equivalent can be obtained by dividing the solid content of the copolymer by the number of moles of epoxy groups contained in the 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 general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group.

R ² represents a direct bond or a divalent organic group. Examples of the organic group include a chain or cyclic saturated or unsaturated hydrocarbon group, -O-, -CO-, -COO-, -NH-, -S-, -SO-, -SO ₂ -, and these The divalent group etc. which consist of a combination of are mentioned.

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 an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a propylene group, an ethylidene group, a propylidene group, and an isopropylidene group, and a vinyl group. A rene group, a propenylene group, a vinylidene group, etc. are mentioned.

Examples of the alicyclic hydrocarbon group include cycloalkylene groups such as a 1,2-cyclopentylene group, a 1,2-cyclohexylene group, a cyclopentylidene group, and a cyclohexylidene group.

Examples of the aromatic hydrocarbon group include a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group, a benzylidene group, a cinnamylidene group, and a biphenylylene group.

In the 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 have a substituent further.

Specifically, as the divalent organic group, for example, -R-, -CO-, -CO-R-, -R-CO-R'-, -COO-, -COO-R-, -R -COO-R'-, -O-R-, -R-O-R'- (wherein R and R' are the same or different and represent the above divalent hydrocarbon group); and the like.

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

Especially, it is preferable that R< ² > is -R-, -COO-, -COO-R-, -COO-, -COO-R- (R is a C1-C4 hydrocarbon group which may have a substituent) and preferably represents an alkylene group having 1 to 2 carbon atoms.) is more preferred.

X represents an epoxy group-containing group. In the present specification, the epoxy group-containing group is a group containing an oxirane ring (epoxy group), such as a glycidyl group in which an oxirane ring is bonded to carbon, or a glycidyl ether group and a glycidyl ester group. A group containing an ether bond or an ester bond, an alicyclic epoxy group including an epoxycyclohexane ring, and the like are included.

As said epoxy-group containing group, the group represented by the following formula (x1) - (x4) is mentioned preferably, for example.

[Formula 15]

In formula, n is an integer of 0-10, Preferably it is an integer of 0-4, More preferably, it is an integer of 0-2.

m is an integer of 1 to 10, preferably an integer of 2 to 8, more preferably an integer of 3 to 6.

Especially, as X, (x1) is preferable from a reactive point, and (x1) whose n=1 is more preferable.

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

[Formula 16]

(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 general formula (1-1), R ¹ represents a hydrogen atom or a methyl group. Among them, R ¹ is preferably a methyl group.

Examples of the divalent organic group represented by R ⁶ include the same groups as the divalent organic group represented by R ² described above.

The number of carbon atoms in the divalent organic group represented by R ⁶ is preferably 0 to 10, more preferably 1 to 4, still more preferably 1 to 2.

Among these, 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 structural unit (A) can be obtained by polymerizing a monomer component containing a monomer capable of introducing the structural unit (A).

As a monomer which can introduce|transduce the said structural unit (A), the compound represented by the following formula (a) is mentioned, for example.

[Formula 17]

(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 capable of introducing the structural unit (A) include, for example, glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, and β-ethylglycylate (meth)acrylate. Dill, vinylbenzyl glycidyl ether, allyl glycidyl ether, (meth)acrylic acid (3,4-epoxycyclohexyl)methyl, vinylcyclohexene oxide, etc. are mentioned. Especially, glycidyl (meth)acrylate and (3,4-epoxycyclohexyl)methyl (meth)acrylate are preferable, and glycidyl (meth)acrylate is more preferable, and side reactions can be suppressed, and storage stability From the point where an improvement of can be expected, glycidyl methacrylate is more preferable.

The copolymer of this invention may have 1 type, or 2 or more types of said structural unit (A).

In the copolymer of the present invention, the content of the structural unit (A) is preferably 0.1 to 50% by mass, more preferably 0.5% by mass or more, and preferably 1% by mass or more with respect to 100% by mass of all structural units. More preferably, it is more preferably 45% by mass or less, and even more preferably 40% by 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 general formula (2).

In the general formula (2), R ³ represents a hydrogen atom or a methyl group.

R ⁴ represents a direct bond or an organic group. Examples of the organic group represented by R ⁴ include the same groups as the organic group represented by R ² described above.

The number of atoms of the organic group represented by R ⁴ is preferably 1 to 10, more preferably 1 to 8, still more preferably 2 to 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, and -CO-OR- (R is a divalent aliphatic hydrocarbon having 1 to 3 carbon atoms) group), -CO-OR(-O-CO-R')- (R represents a linear or branched divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms. R' is 1 to 3 carbon atoms. Representing a monovalent aliphatic hydrocarbon group of 3.) is more preferable, and -CO-OR- (R represents a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms.) is still more preferable.

R ⁵ represents a bonded chain having a length of 2 atoms or more. The length of the linkage chain is the number of atoms arranged on the main chain of the linkage chain, and the number of atoms constituting the side chain of the linkage chain is not included. Specifically, for example, as a bonded chain having a length of 2 atoms, -CH ₂ -CH ₂ -, -C(CH ₃ )-CH ₂ -, -C(CH ₃ )-C(CH ₃ )- , -CH ₂ -O-, -O-CH ₂ -, -CO-O-, -CH=CH-, and the like, and examples of the 3-membered bonded chain include -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 linkage chain is 0, it has the same meaning as “direct linkage”.

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

It is preferable that the said bond chain is a divalent organic group. As said divalent organic group, the same group as the divalent organic group represented by R< ² > mentioned above is mentioned, for example.

Among them, the organic group is -R-, -O-R-, -O-R-O-, -CO-R-, -O-R-O-CO-R'- (R and R' are the same or different, and may have a substituent represents a divalent hydrocarbon group.) is preferred, and is -R-, -O-R-, -O-R-O-CO-R'- (R and R' are the same or different, and represent a divalent aliphatic hydrocarbon group which may have a substituent ) is more preferred, and an ethylene group is still more preferred.

Y represents an acidic radical. Examples of the acid group include a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group, and other functional groups capable of neutralizing reaction with alkaline water. You may have it. Especially, a carboxyl group or a carboxylic anhydride group is preferable, and a carboxyl group is more preferable.

Moreover, you may have 2 or more acidic radicals.

a represents 0 or 1. It is preferable that a is 1 from the viewpoint of further excellent solvent resistance.

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

[Formula 18]

(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 from the viewpoint of improving the heat resistance and developability of the polymer.

As the organic group represented by R ⁷ and R ⁸ , the aforementioned divalent organic groups and the like are preferably used. Among them, as R ⁷ , a divalent hydrocarbon group which may have a substituent is preferable, and may have a substituent. A divalent aliphatic hydrocarbon group is more preferable, and an alkylene group is still more preferable.

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 groups represented by R ⁷ and R ⁸ is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3.

Although b represents 0 or 1, it is preferable that it is 1 from the point which solvent resistance can further improve.

The copolymer having the structural unit (B) is a base polymer obtained by polymerizing a monomer component containing a monomer capable of introducing the structural unit (B) or polymerizing a monomer component containing a hydroxyl group-containing monomer. It can be obtained by reacting an acid group-containing compound.

Examples of the monomer capable of introducing the structural unit (B) include β-carboxyethyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, and mono(2-methacryloyl) succinate. long-chain unsaturated monocarboxylic acids in which a chain is extended between an unsaturated group such as oxyethyl) and a carboxyl group; and the like.

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

[Formula 19]

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

Specific examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, Hydroxyalkyl (meth)acrylates, such as 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2,3-hydroxypropyl (meth)acrylate; Glycerin mono(meth)acrylate, trimethylolpropanemono(meth)acrylate, mono(meth)acrylate of pentaerythritol, ditrimethylolpropane mono(meth)acrylate and dipentaerythritol mono(meth)acrylate mono(meth)acrylates of polyols such as the like; Hydroxyalkyl acrylamides, such as N-hydroxyethyl acrylamide, are mentioned.

Examples of the acid group-containing compound include compounds represented by the following formula (b2) or formula (b3).

[Formula 20]

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

[Formula 21]

(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 trimellitic acid; carboxylic acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, and trimellitic anhydride; etc. can be mentioned. Among them, carboxylic acid anhydrides are preferred, and succinic anhydride is more preferred, from the viewpoint of higher addition reactivity.

A specific method for obtaining a copolymer having the structural unit (B) will be described in detail in the method for producing a polymer described later.

The copolymer of this invention may have 1 type, or 2 or more types of structural units (B).

In the copolymer of the present invention, the content 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 or more with respect to 100% by mass of all structural units. More preferably, it is more preferably 45% by mass or less, and even more preferably 40% by mass or less.

＜Structural unit (C)＞

It is preferable that the copolymer of this invention is also a copolymer which has a cyclic structure in a main chain. That is, it is preferable that the said copolymer further has the structural unit (C) which has a cyclic structure in a principal chain. If the copolymer is a polymer having a cyclic structure in the main chain, a cured product having excellent heat resistance can be provided.

As said ring structure, an imide ring, a tetrahydropyran ring, a tetrahydrofuran ring, a lactone ring, etc. are mentioned.

A copolymer having the structural unit (C) can be obtained by polymerizing a monomer component containing a monomer capable of introducing a ring structure into the main chain.

Examples of the monomer capable of introducing a cyclic structure into the main chain include, for example, a monomer having a double bond-containing cyclic structure in the molecule, a monomer that undergoes cyclization polymerization to form a polymer having a cyclic structure in the main chain, and after polymerization and monomers forming a ring structure. From the viewpoint of good heat resistance, hardness, colorant dispersibility, etc., specifically, N-substituted maleimide-based monomers, dialkyl-2,2'-(oxydimethylene) diacrylate-based monomers, and α-(unsaturated alkoxy At least one type of monomer selected from the group consisting of alkyl) acrylate-based monomers is preferably used. Among them, N-substituted maleimide-based monomers are preferred from the viewpoint of further excellent solvent resistance.

Examples of the N-substituted maleimide-based monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, and N-t-butylmaleimide. Mead, N-dodecyl maleimide, N-benzyl maleimide, N-naphthyl maleimide, etc. are mentioned, One type or two or more types of these can be used. Especially, from a heat resistant viewpoint, N-phenyl maleimide, N-benzyl maleimide, and N-cyclohexyl maleimide are preferable, and N-benzyl maleimide is more preferable.

Examples of the N-benzyl maleimide include benzyl maleimide; Alkyl-substituted benzyl maleimide, such as p-methylbenzyl maleimide and p-butylbenzyl maleimide; phenolic hydroxyl group-substituted benzylmaleimides such as p-hydroxybenzylmaleimide; halogen-substituted benzyl maleimides such as o-chlorobenzyl maleimide, o-dichlorobenzyl maleimide, and p-dichlorobenzyl maleimide; etc. can be mentioned.

Examples of the dialkyl-2,2'-(oxydimethylene)diacrylate-based monomer include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl -2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di( Isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-butyl)-2,2'-[oxybis(methylene)]bis-2-propenoate , di(isobutyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(t-butyl)-2,2'-[oxybis(methylene)]bis-2- Propenoate, di(t-amyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(stearyl)-2,2'-[oxybis(methylene)]bis -2-propenoate, di(lauryl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2'-[oxybis( methylene)] bis-2-propenoate and the like. Among these, from the viewpoints of transparency, dispersibility, industrial availability and the like, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate is more preferable.

Examples of the α-(unsaturated alkoxyalkyl)acrylate-based monomer include α-(allyloxymethyl)acrylate-based monomers.

Specific examples of the α-(allyloxymethyl) acrylate monomer include α-allyloxymethyl acrylic acid; α-allyloxymethyl methyl acrylate, α-allyloxymethyl ethyl acrylate, α-allyloxymethyl acrylate n-propyl, α-allyloxymethyl acrylate i-propyl, α-allyloxymethyl acrylate n-butyl, α-allyloxy s-butyl methyl acrylate, α-allyloxymethyl t-butyl acrylate, α-allyloxymethyl acrylate n-amyl, α-allyloxymethyl s-amyl acrylate, α-allyloxymethyl t-amyl acrylate, α-allyloxy Methyl acrylate n-hexyl, α-allyloxymethyl acrylate s-hexyl, α-allyloxymethyl acrylate n-heptyl, α-allyloxymethyl acrylate n-octyl, α-allyloxymethyl acrylate s-octyl, α-allyloxy Methyl acrylate t-octyl, α-allyloxymethyl acrylate 2-ethylhexyl, α-allyloxymethyl acrylate capryl, α-allyloxymethyl acrylate nonyl, α-allyloxymethyl decyl acrylate, α-allyloxymethyl acrylate undecyl , α-allyloxymethyl lauryl acrylate, α-allyloxymethyl tridecyl acrylate, α-allyloxymethyl acrylate myristyl, α-allyloxymethyl acrylate pentadecyl, α-allyloxymethyl acrylate, α-allyloxy Heptadecyl methyl acrylate, α-allyloxymethyl stearyl acrylate, α-allyloxymethyl acrylate nonadecyl, α-allyloxymethyl acrylate, α-allyloxymethyl seryl acrylate, α-allyloxymethyl melissyl acrylate, etc. alkyl-(α-allyloxymethyl) acrylate-based monomers; α-allyloxymethyl methoxyethyl acrylate, α-allyloxymethyl methoxyethoxyethyl acrylate, α-allyloxymethyl methoxyethoxyethoxyethyl acrylate, α-allyloxymethyl 3-methoxybutyl acrylate, α- Alkoxyalkyl-(α-allyl, such as allyloxymethyl ethoxyethyl acrylate, α-allyloxymethyl ethoxyethoxyethyl acrylate, α-allyloxymethyl phenoxyethyl acrylate, α-allyloxymethyl phenoxyethoxyethyl acrylate, etc. oxymethyl) acrylate-based monomers; α-allyloxymethyl hydroxyethyl acrylate, α-allyloxymethyl hydroxypropyl acrylate, α-allyloxymethyl hydroxybutyl acrylate, α-allyloxymethyl fluoroethyl acrylate, α-allyloxymethyl acrylate difluoroethyl , α-allyloxymethyl chloroethyl acrylate, α-allyloxymethyl dichloroethyl acrylate, α-allyloxymethyl bromoethyl acrylate, α-allyloxymethyl dibromoethyl acrylate, α-allyloxymethyl vinyl acrylate, α- Allyloxymethyl allyl acrylate, α-allyloxymethyl metharyl acrylate, α-allyloxymethyl crotyl acrylate, α-allyloxymethyl propargyl acrylate, α-allyloxymethyl cyclopentyl acrylate, α-allyloxymethyl cycloacrylate Hexyl, α-allyloxymethyl acrylate 4-methylcyclohexyl, α-allyloxymethyl acrylate 4-t-butylcyclohexyl, α-allyloxymethyl acrylate tricyclodecanyl, α-allyloxymethyl acrylate isobornyl, α -Allyloxymethyl adamantyl acrylate, α-allyloxymethyl acrylate dicyclopentadienyl, α-allyloxymethyl acrylate, α-allyloxymethyl methylphenyl acrylate, α-allyloxymethyl dimethyl acrylate, α-allyloxy Trimethylphenyl methyl acrylate, α-allyloxymethyl 4-t-butylphenyl acrylate, benzyl α-allyloxymethyl acrylate, diphenylmethyl α-allyloxymethyl acrylate, diphenylethyl α-allyloxymethyl acrylate, α-allyloxy Triphenylmethyl methyl acrylate, α-allyloxymethyl cinnamyl acrylate, α-allyloxymethyl naphthyl acrylate, α-allyloxymethyl anthranil acrylate; etc. can be mentioned. Especially, the alkyl-((alpha)-allyloxymethyl) acrylate type monomer is preferable. As the alkyl-(α-allyloxymethyl)acrylate-based monomer, from the viewpoint of transparency, dispersibility, industrial availability, etc., α-allyloxymethylmethyl acrylate (methyl-(α-allyloxymethyl)acrylic acid Also referred to as rate) is particularly preferred.

The said α-(unsaturated alkoxyalkyl)acrylate can be manufactured by the manufacturing method disclosed in the pamphlet of International Publication No. 2010/114077, for example.

As the monomer capable of introducing a cyclic structure into the main chain, 2-(hydroxyalkyl) alkyl acrylate esters are preferably used. 2-(Hydroxyalkyl)acrylic acid alkyl ester can react with (meth)acrylic acid to form a lactone ring structure in the main chain.

As said 2-(hydroxyalkyl) alkyl acrylate ester, 2-(1-hydroxyalkyl) acrylate alkyl ester and 2-(2-hydroxyalkyl) acrylate alkyl ester are mentioned, Specifically, For example, For example, 2-(1-hydroxymethyl) methyl acrylate, 2-(1-hydroxymethyl) ethyl acrylate, 2-(1-hydroxymethyl) isopropyl acrylate, 2-(1-hydroxymethyl) acrylate n -Butyl, 2-(1-hydroxymethyl) t-butyl acrylate, 2-(1-hydroxymethyl) 2-ethylhexyl acrylate, etc. are mentioned. Especially, 2-(1-hydroxymethyl) methyl acrylate and 2-(1-hydroxymethyl) ethyl acrylate are preferable. These may be used individually by 1 type, and may be used in combination of 2 or more type.

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

In the copolymer, the content of the structural unit (C) is preferably 0.1 to 50% by mass, more preferably 0.2% by mass or more, and still more preferably 1% by mass or more, based on 100% by mass of all 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) other than the structural unit (A), (B), and (C) mentioned above. Examples of the structural unit (D) include, in addition to the above-mentioned hydroxyl group-containing monomers, acid group-containing monomers other than the above-mentioned long-chain unsaturated monocarboxylic acids, (meth)acrylic acid ester-based monomers, and groups having an acid group-generating group. and structural units derived from monomers 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 vinylbenzoic acid; unsaturated polyhydric carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; phosphoric acid group-containing unsaturated compounds such as Light Ester P-1M (manufactured by Kyoeisha Chemical); etc. can be mentioned.

Examples of the (meth)acrylic acid ester monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, and n-butyl (meth)acrylate. , (meth)acrylate s-butyl, (meth)acrylate n-amyl, (meth)acrylate s-amyl, (meth)acrylate n-hexyl, (meth)acrylate 2-ethylhexyl, (meth)acrylate isodecyl, ( Tridecyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylate ) 1-adamantyl acrylate, (meth)acrylate (3,4-epoxycyclohexyl)methyl, (meth)acrylate dicyclopentanyl, (meth)acrylate dicyclopentenyl, (meth)acrylate benzyl, (meth)acrylic acid 2-methoxyethyl, 2-ethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, 1,4-dioxaspiro[4,5]deca-2-ylmethacrylic acid, (meth)acryloylmorpholine, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1, 3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-cyclo Hexyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, etc. are mentioned.

Examples of the monomer having a group generating an acid group include a compound having a polymerizable double bond and a group generating an acid group by heat or an acid. 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 groups generating acid groups by heat or acid include tertiary carbon-containing groups, groups whose acid groups are blocked by vinyl ether compounds, and phenolic hydroxyl groups protected by protective groups such as t-butyl and acetyl groups. and the like.

As the tertiary carbon-containing group, preferably, a group represented by -COO ^* R ^a (R ^a represents a monovalent organic group, and the carbon atom bonded to O ^* is a tertiary carbon atom) is exemplified. . By heating, the OC bond between -COO ^* and R ^a is cleaved, and a carboxyl group is generated.

R a of the above -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 with three other carbon atoms bonded to the carbon atom.

As the monovalent organic group, preferably, a monovalent chain, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 91 carbon atoms is used. The organic group may have a substituent.

The number of carbon atoms of R ^a is more preferably 1 to 50 carbon atoms, still more preferably 1 to 35 carbon atoms, still more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, most preferably is 1 to 9 carbon atoms.

R ^a can preferably be represented by -C(R ^b )(R ^c )(R ^d ). In this case, R ^b , R ^c , and R ^d are the same or different, and it is preferable that they are hydrocarbon groups of 1 to 30 carbon atoms. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, may have a cyclic structure, or may have a substituent. Moreover, R ^b , R ^c , and R ^d may be connected to each other at the terminal site to form a cyclic structure.

Here, in the tertiary carbon-containing group, it is preferable that at least one of the adjacent carbon atoms of the tertiary carbon atom is bonded to a hydrogen atom. For example, when R ^a is a group represented by -C(R ^b )(R ^c )(R ^d ), at least one of R ^b , R ^c and R ^d is a carbon atom having at least one hydrogen atom. It is included, and it is preferable that the carbon atom is bonded to a tertiary carbon atom.

R ^b , R ^c and R ^d are the same or different, preferably a saturated hydrocarbon group of 1 to 15 carbon atoms, more preferably a saturated hydrocarbon group of 1 to 10 carbon atoms, still more preferably a saturated hydrocarbon group of 1 to 5 carbon atoms A saturated hydrocarbon group, particularly preferably a saturated hydrocarbon group having 1 to 3 carbon atoms.

Said R ^a is preferably a t-butyl group or a t-amyl group.

As the tertiary carbon-containing monomer, preferably t-butyl (meth)acrylate, t-amyl (meth)acrylate and the like are exemplified.

Examples of the group in which the acid group is blocked by the vinyl ether compound include a group in which a vinyl ether compound is bonded to the above acid group such as a carboxyl group.

Examples of the vinyl ether compound include methyl vinyl ether, ethyl vinyl ether, i-propyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, 2 - Aliphatic vinyl ether compounds, such as ethylhexyl vinyl ether and cyclohexyl vinyl ether, and cyclic ether compounds, such as dihydropyran, which can form vinyl ether by ring-opening, etc. are mentioned.

Among the above-mentioned vinyl ether compounds, dihydropyran is preferred because the protecting group is easily desorbed at a lower temperature.

As the group in which the acid group is blocked by the dihydropyran, a group preferably represented by the following formula is exemplified.

[Formula 22]

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

[Formula 23]

(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 in the presence of an acid catalyst such as hydrochloric acid or sulfuric acid at a temperature of 50 to 150°C for 1 to 30 hours, whereby the protective group is desorbed and an acid group is generated.

Specific examples of the monomer having a group represented by the above formula include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, Monomers in which the hydroxyl group of an aromatic vinyl compound having a phenolic hydroxyl group such as o-isopropenylphenol is protected by a t-butyl group or an acetyl group are exemplified.

Among them, as the monomer having a group capable of generating an acid group, a monomer having a group in which an acid group is blocked by the dihydropyran is preferable since it can generate an acid group at a lower temperature.

As said other monomer which can be copolymerized, the 1 type(s) or 2 or more types of the following compounds etc. are mentioned, for example.

(meth)acrylamides such as N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, and N-isopropylacrylamide; macromonomers having (meth)acryloyl groups at one end of polymer molecular chains, such as polystyrene, polymethyl (meth)acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, and polycaprolactam; conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; Aromatic vinyls, such as styrene, vinyltoluene, (alpha)-methylstyrene, xylene, methoxy styrene, and ethoxy styrene; 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 vinyl ethers such as methoxyethoxyethyl vinyl ether, methoxy polyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, and 4-hydroxybutyl vinyl ether; N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, and N-vinylacetamide; unsaturated isocyanates such as isocyanatoethyl (meth)acrylate and allyl isocyanate; etc. can be mentioned.

Among them, as a monomer that imparts the structural unit (D), for example, by copolymerizing a monomer having an amide group such as the above-mentioned (meth)acrylamides, addition reaction can be carried out without using a basic catalyst such as an amine. Therefore, the storage stability of the copolymer can be improved.

In addition, even when using a monomer having an amine group such as N,N-dimethylaminoethyl (meth)acrylate or N,N-diethylaminoethyl (meth)acrylate, the addition reaction can be carried out without using a catalyst. , it is possible to improve the storage stability of the copolymer.

Moreover, as a monomer which provides the said 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 point which gelation is suppressed and storage stability becomes favorable.

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 side chain may be linear or branched. Specific examples of the monomer having a long side chain include preferably 2-ethylhexyl (meth)acrylate.

Examples of the monomers having a large steric hindrance include those having a ring structure in the side chain, and examples thereof include cyclohexyl, bicyclo, phenyl, biphenyl, dicyclopentanyl, furan, pyran, piperidine, and the like. It can be mentioned that it has the structure of Specific examples of the monomer having high steric hindrance include, for example, vinyltoluene, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (meth)acrylate phenoxyethyl (meth)acrylate, (meth)acrylic acid, (meth)acrylate dicyclopentanyl, (meth)acrylate dicyclopentenyl, (meth)acrylate tricyclodecanyl, (meth)acrylate isobor Nyl, (meth)acrylate pentamethylpiperidinyl, etc. are mentioned. Especially, dicyclopentanyl (meth)acrylate, vinyltoluene, benzyl (meth)acrylate, and cyclohexyl (meth)acrylate are preferable.

Especially, the said copolymer is at least 1 sort(s) selected from the group which consists of vinyl toluene, 2-ethylhexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate from the point which storage stability can further improve. It is preferable to have a structural unit derived from the monomer of Moreover, when the said copolymer has a 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 units (D).

In the copolymer, the content of the structural unit (D) is preferably 0.1 to 50% by mass, more preferably 0.2% by mass or more, and even more preferably 1% by mass or more with respect to 100% by mass of all 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 copolymer is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, and still more preferably 30 mgKOH/g or more. Further, it is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, still more preferably 200 mgKOH/g or less, and still more preferably 100 mgKOH/g or less.

The said acid value is a value obtained by measuring by the neutralization titration method using a potassium hydroxide (KOH) solution, and is an acid value per 1 g of polymer solid content.

It is preferable that it is 2000 or more, as for the weight average molecular weight of the said copolymer, it is more preferable that it is 3000 or more, and it is still more preferable that it is 4000 or more. Moreover, it is preferably 250000 or less, more preferably 100000 or less, still more preferably 50000 or less, and still more preferably 20000 or less.

The weight average molecular weight of the copolymer can be measured by a gel permeation chromatography (GPC) method, and can be specifically measured by the method described in Examples.

The said copolymer may have a polymerizable double bond (carbon-carbon double bond) in a side chain. The photocurability of the copolymer can be improved by having a polymerizable double bond in the side chain. Although what was mentioned above is mentioned as said polymerizable double bond, Among these, a (meth)acryloyl group is preferable.

When the said copolymer has a polymerizable double bond in a side chain, it is preferable that the double bond equivalent of the said copolymer is 200-20000 g/equivalent. The double bond equivalent weight is more preferably from 250 to 15000 g/equivalent, more preferably from 300 to 10000 g/equivalent, and even more preferably from 300 to 4000 g/equivalent from the viewpoint of improving curability. do.

The said double bond equivalent is the mass of the solid content of the polymer solution per 1 mol of double bonds of the said copolymer. The solid mass of the polymer solution is the sum of the mass of the monomer components constituting the copolymer and the mass of the polymerization inhibitor. The double bond equivalent can be obtained by dividing the mass (g) of the polymer solid content of the polymer solution by the amount of double bonds (mol) in the copolymer. The amount of double bonds in the copolymer can be obtained from the amount of the monomer containing an acid group used during polymerization and the amount of a compound having a polymerizable double bond. Moreover, it can also measure using various analyzes, such as titration and elemental analysis, NMR, IR, and a differential scanning calorimetry method. For example, it may be calculated by measuring the number of ethylenic double bonds contained per 1 g of the copolymer in accordance with the test method for iodine value described in JIS K 0070:1992.

<Method for producing copolymer>

The method for producing the copolymer of the present invention is not particularly limited as long as it is a method capable of obtaining a copolymer having at least the above-mentioned structural units (A) and structural units (B) and having an epoxy equivalent within a predetermined range. , For example, a method of polymerizing a monomer component including a monomer capable of introducing each structural unit described above, or a base polymer is obtained by polymerizing the monomer component, and an addition reaction of another compound to a group of the base polymer is performed. , a method of obtaining a polymer having a predetermined structural unit, and the like.

A method of polymerizing the monomer components is not particularly limited, and commonly used methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used. Among them, solution polymerization is preferable because it is industrially advantageous and structural adjustment such as molecular weight is easy. In addition, as the polymerization mechanism of the monomer component, a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, etc. can be used, but from an industrial point of view, a polymerization method based on a radical polymerization mechanism this is preferable

In addition, the molecular weight of the polymer obtained by polymerizing the monomer components can be controlled by appropriately adjusting the amount or type of polymerization initiator, polymerization temperature, and type or amount of chain transfer agent.

As said polymerization initiator, peroxides, azo compounds, etc. normally used as a polymerization initiator are mentioned. As said chain transfer agent, the compound etc. which have a mercapto group, such as the alkyl mercaptans normally used as a chain transfer agent, mercaptocarboxylic acids, and mercaptocarboxylic acid esters, are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, these addition amounts can be set suitably from a well-known method.

Examples of the solvent used for the polymerization include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; Ketones, such as acetone and methyl ethyl ketone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; Aromatic hydrocarbons, such as toluene, xylene, and ethylbenzene; chloroform; dimethyl sulfoxide; Dimethyl carbonate etc. are mentioned. You may use these solvent individually or in combination of 2 or more types.

The polymerization concentration when polymerizing the monomer composition (reaction liquid) containing the above monomer components is preferably 5 to 90% by mass, more preferably 5 to 70% by mass, still more preferably 10 to 60% by mass % am. The said polymerization concentration is the mass % of the monomer used with respect to 100 mass % of a reaction liquid.

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

As a method for producing the copolymer, for example, step (1) of polymerizing a monomer component containing an epoxy group-containing monomer represented by the formula (a) and a hydroxyl group-containing monomer represented by the formula (b1); and , A method including step (2) of reacting the polymer obtained in the polymerization step (1) with the acid group-containing compound represented by the formula (b2) or formula (b3) is preferably used.

By producing the copolymer in this way, it is possible to suppress gelation during production of the copolymer, and a copolymer having the structural unit (A) and the structural unit (B) can be obtained efficiently.

That is, the present invention further relates to a step (1) of polymerizing a monomer component containing an epoxy group-containing monomer represented by formula (a) and a hydroxyl group-containing monomer represented by formula (b1), and the polymerization step (1) obtained A method for producing a copolymer characterized by including a step (2) of reacting the polymer with the acid group-containing compound represented by the formula (b2) or formula (b3).

Each process in the said manufacturing method is demonstrated.

process (1)

In the copolymer production method of the present invention, a monomer component containing the epoxy group-containing monomer represented by the formula (a) and the hydroxyl group-containing monomer represented by the formula (b1) is polymerized.

As an epoxy group-containing monomer represented by the said formula (a), the monomer etc. described as the monomer which can introduce|transduce the structural unit (A) of the above-mentioned copolymer etc. are mentioned, for example. What was mentioned above is mentioned as said hydroxyl-containing monomer represented by said formula (b1).

The content ratio of the epoxy group-containing monomer and the hydroxyl group-containing monomer is not particularly limited, and may be appropriately set so that the content ratio of the above-mentioned structural unit (A) and structural unit (B) is obtained in the resulting copolymer.

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

A method of polymerizing the monomer component is not particularly limited, and may be polymerized by the known method described above. The polymerization temperature and time are as described above.

In the above polymerization, a commonly used polymerization initiator, chain transfer agent, catalyst, solvent, or the like may be used.

process (2)

Next, the process of making the polymer obtained at the said process (1) and the acidic radical containing compound represented by the said formula (b2) or formula (b3) react is included.

By reacting the polymer (base polymer) obtained in the step (1) with the acid group-containing compound represented by the formula (b2) or (b3), the hydroxyl group of the polymer (base polymer) obtained in the step (1) is converted to the acid group. A containing compound can be added to form a long-chain acid group.

The reaction method is not particularly limited, and a known method can be used.

As reaction temperature, 25-100 degreeC is preferable, for example, and 30-90 degreeC is more preferable.

Although it does not specifically limit as reaction time, For example, 1 to 20 hours are mentioned.

In addition, the step of reacting the acid group-containing compound may be performed in the presence of a basic compound. By carrying out the reaction in the presence of a basic compound, the reaction between the hydroxyl group and the acid group can be carried out under lower temperature conditions such as 70°C or lower. In addition, since the reaction is carried out under the low-temperature conditions as described above, 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 proceed, and the copolymer having the structural unit (A) and the structural unit (B) can be obtained. can be produced more efficiently.

For example, in step (2), the polymer (base polymer) obtained in step (1) and the acid group-containing compound may be reacted in the presence of a basic compound at 70°C or less. In this case, when the temperature exceeds 70°C, the reaction between the epoxy group and the acid group tends to proceed, and there is a possibility that the resin may gel.

Examples of the acid group-containing compound represented by the formula (b2) or formula (b3) include the acid group-containing compounds described above.

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 dimethylethanolamine, n-butylamine, and diethylamine; Cyclic aliphatic amines, such as cyclohexylamine; heterocyclic amines such as piperidine, morpholine, N-ethylpiperidine, N-ethylmorpholine, and pyridine; aromatic amines such as benzylamine, N-methylaniline, and N,N-dimethylaniline; tetraalkylammonium halides such as tetramethylammonium chloride and tetraethylammonium chloride; tetraalkylammonium organic acid salts such as tetramethylammonium acetate; tetraalkylammonium inorganic acid salts such as tetramethylammonium hydrogen sulfate and tetraethylammonium hydrogen sulfate; (hydroxy)alkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and monohydroxyethyltrimethylammonium hydroxide; hydroxides of alkali metals such as sodium and potassium; Hydroxide of transition metals, such as barium, strontium, calcium, and lanthanum; free salts of complex salts such as [Pt(NH ₃ ) ₆ ](OH) ₄ ; and phosphorus compounds such as triphenylphosphine, tricyclohexylphosphine, and trimethylphosphine. Among them, from the viewpoint of ease of production and ease of handling, secondary amines, tertiary amines, heterocyclic amines, and phosphorus compounds are preferable, and side reactions can be suppressed, and the increase in molecular weight of the polymer after addition can be suppressed. From the viewpoint of possibility, it is more preferable that they are tertiary amines and triphenylphosphine.

The amount of the basic compound used is not particularly limited, but from the viewpoint of reaction efficiency, it is preferably 0 to 5 mol%, more preferably 0 to 4 mol%, based on 100 mol% of the acid group-containing compound. , more preferably 0 to 3 mol%.

The amount of the acid group-containing compound used is appropriately set so that the content of the structural unit (B) falls within a desired range or the acid value of the copolymer falls within a desired range, depending on the purpose and use of the copolymer to be obtained. do.

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

In the above reaction, you may use a catalyst, solvent, etc. normally used.

Further, in order to produce a copolymer having a polymerizable double bond in the side chain, after the step (1) above, an acid group-containing monomer or an isocyanate group-containing polymerizable monomer is subjected to an addition reaction to the hydroxyl group, or the step (1) or ( 2) After that, a polymerizable double bond can be introduced into the side chain of the copolymer by subjecting the acid group-containing monomer to an addition reaction to the epoxy group.

As said acid group containing monomer, what was mentioned above is mentioned, Preferably (meth)acrylic acid is mentioned.

Examples of the isocyanate group-containing polymerizable monomer include the above-mentioned unsaturated isocyanates, and (meth)acrylic acid is preferable from the viewpoint that an addition reaction can be performed at a low temperature and the storage stability of the copolymer can be improved. Isocyanatoethyl is mentioned.

The addition reaction is not particularly limited and can be carried out by a known method.

In the above addition reaction, a commonly used compound, catalyst, solvent, or the like may be used.

Among them, as the catalyst, the above-described 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. desirable. In addition, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltindilaurate, dioctyltindi, which are generally used as reaction catalysts between isocyanate monomers and hydroxyl groups. Tin-based compounds such as laurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin acetate, dioctyltin oxide, and tributyltin chloride can also be preferably used.

The manufacturing method of the said copolymer may include other processes other than the reaction process mentioned above. For example, an aging process, a neutralization process, a polymerization initiator or chain transfer agent deactivation process, a dilution process, a drying process, a concentration process, a purification process, etc. are mentioned. These steps can be performed by known methods.

2. Copolymer solution

The present invention is also a copolymer solution characterized by containing the above-described copolymer and a protic polar solvent. The copolymer solution of the present invention is excellent in storage stability.

As described above, the copolymer has an acid group and an epoxy group, and since these groups are highly reactive, it is difficult to secure storage stability while curing the copolymer at low temperatures. The present inventors have found that the storage stability of the copolymer can be improved by adding a protic polar solvent, and both high solvent resistance and storage stability can be achieved.

Although the reason why the storage stability of the copolymer is improved by the addition of the protic polar solvent is not clear, in the copolymer, the presence of an acid group such as a carboxyl group at a position separated from the main chain increases the protic polar solvent. It is estimated that this is because hydrogen bonds are relatively easily made with the acid group, the anionic property of the acid group is lowered, and the reactivity of the acid group and the epoxy group is suppressed.

<Protonic polar solvent>

Examples of the protic polar solvent include water, alcohol solvents, amine solvents, and phenol solvents. Especially, it is preferable that the said protic polar solvent is an alcoholic solvent.

As said alcohol solvent, saturated alcohol is mentioned preferably, and monofunctional alcohol (monoalcohol), polyhydric alcohol, glycol monoether, etc. are mentioned.

Specific examples of the alcohol 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, diethylene glycol mono-n-propyl ether, di primary alcohols such as ethylene glycol mono-n-butyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol mono-n-butyl ether, tripropylene glycol, and tripropylene glycol mono-n-butyl ether;

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 secondary alcohols such as ether, dipropylene glycol mono-n-butyl ether, or tripropylene glycol monomethyl ether;

and tertiary alcohols such as tert-butanol, tert-pentanol, and tert-hexanol.

Especially, it is preferable that the said alcohol solvent is a secondary alcohol or a tertiary alcohol from the point which can suppress reactivity with an epoxy group and reduce the viscosity of a copolymer solution.

The number of carbon atoms in the alcoholic solvent is preferably 1 to 10, more preferably 2 to 8, still more preferably 3 to 6, from the viewpoint of having a relatively low boiling point and being easily removed by heating.

As the alcohol solvent, propylene glycol monomethyl ether is particularly preferred.

Examples of the amine solvent include diethyleneamine, dimethylamine, and oleylamine.

Examples of the phenolic solvent include phenol, cresol, o-cresol, m-cresol, p-cresol, and xylenol.

As for the said protic polar solvent, only 1 type may be used, and 2 or more types may be used together.

The boiling point of the protic polar solvent is preferably 70 to 170 ° C., and more preferably 100 to 160 ° C., from the viewpoint of being easily removed by heating, having a boiling point to a certain extent, and easily forming a flat film. It is preferable, and it is more preferable that it is 120-150 degreeC.

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

In terms of stability, the copolymer solution preferably further contains, in addition to the protic polar solvent, another solvent capable of hydrogen bonding. As said other solvent, N,N- dimethylformamide etc. are mentioned, for example.

Moreover, as a solvent for adjusting the concentration, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; Aromatic hydrocarbons, such as toluene, xylene, and ethylbenzene; chloroform; dimethyl sulfoxide; etc. may be included.

When the copolymer solution contains a solvent other than the protonic polar solvent, the content of the protonic polar solvent is 5 parts by mass or more with respect to 100 mass% of the total amount of the protonic polar solvent and the other solvent. It is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less.

The copolymer solution may be prepared by mixing a copolymer obtained during polymerization and purified from a polymerization solution containing the copolymer with the protic polar solvent, wherein the proton is added to the polymerization solution containing the copolymer. You may prepare by adding a polar solvent. When preparing by adding the protic polar solvent to the polymerization solution containing the copolymer, the copolymer solution may contain the polymerization solvent.

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

<Acid compound>

The copolymer solution may further contain an acid compound having a pKa of 4.2 or less.

When the copolymer solution contains an acid compound having a pKa of 4.2 or less, the reaction between the acid group and the epoxy group of the copolymer is suppressed, and the storage stability of the copolymer can be further improved. The storage stability of the copolymer can be improved by including an acid compound having a pKa of 4.2 or less by the presence of an acid compound having stronger acid strength than the acid groups capable of forming the acid group-containing structural unit (B) of the copolymer. , It is considered that the anionicity of the acid group in the copolymer is lowered, 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, an acid compound having a pKa of 4.2 or less captures the basic compound that has formed a salt with a carboxyl group, and the nucleophilic force of the carboxyl group in the copolymer is lowered, It is thought that the reactivity of the said acid group and an epoxy group can be suppressed.

The reason why the pKa was set to 4.2 or less is that the pKa value of the monomer capable of introducing the structural unit (B) or the monomer containing an acid group was set as a critical value. As the pKa value of the monomer, for example, acrylic acid (pKa 4.35), methacrylic acid (pKa 4.26), succinic acid mono(2-acryloyloxyethyl) (pKa 4.35), succinic acid mono(2-methacryloyl) yloxyethyl) (pKa 4.35); and the like.

It is preferable that it is 3 or less, and, as for the pKa of the said acid compound, it is more preferable that it is 2 or less. Although the lower limit of pKa of the said acid compound is not specifically limited, It is preferable that it is -3 or more, and it is more preferable that it is 0 or more.

pKa (acid dissociation constant) means the negative common logarithm (logarithm of the reciprocal) of the equilibrium constant Ka in a dissociation reaction in which hydrogen ions are released from an acid, and particularly means a value in water at 25°C.

For the value of pKa, reference can be made to literature such as Chemical Handbook, Fundamentals II (revised 5th edition, Maruzen Co., Ltd.), and numerical values not published in the literature can be calculated by the method described in the literature. can

Specific examples of the acid compound having a pKa of 4.2 or less include, for example, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid, phosphinic acid, pyrophosphoric acid, polyphosphoric acid, sulfuric acid, sulfurous acid, thiosulfuric acid, Dimethylsulfurous acid, diethylsulfurous acid, dipropylsulfurous acid, dibutylsulfurous acid, diphenylsulfuric acid, dimethylsulfuric acid, diethylsulfuric acid, dipropylsulfuric acid, dibutylsulfuric acid, diphenylsulfuric acid, benzenesulfinic acid, toluenesulfinic acid, naphthalenesulfinic acid, Aromatic sulfonic acids such as benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, diisopropylnaphthalenesulfonic acid and diisobutylnaphthalenesulfonic acid, alkylsulfonic acids such as methylsulfonic acid, ethylsulfonic acid and propylsulfonic acid , α-olefin sulfonic acids, sulfonated polystyrenes, methyl acrylate-sulfonated styrene copolymers, and derivatives thereof.

It is preferable that it is 400 or less, and, as for the molecular weight of the said acid compound, it is more preferable that it is 350 or less. It is preferable that it is 150 or more, and, as for the molecular weight of the said acid compound, it is more preferable that it is 250 or more.

<Phosphoric acid derivative>

The copolymer solution may also contain a phosphoric acid derivative. Storage stability of the copolymer may be improved by further including a phosphoric acid derivative in the copolymer solution.

As said phosphoric acid derivative, phosphoric acid ester, phosphorous acid ester, phosphorous acid, hypophosphorous acid, phosphonic acid, and phosphinic acid are mentioned preferably, and phosphoric acid ester, phosphonic acid, and phosphinic acid are more preferable.

Examples of the ester group of the phosphoric acid ester or phosphorous acid ester include an alkyl ester group, an aryl ester group, an aralkyl ester group, and an ester group having a polymerizable double bond. Examples of the alkyl of the alkyl ester group include methyl, ethyl, octyl, and 2-ethylhexyl. Examples of the aryl of the aryl ester group include phenyl, tolyl, and naphthyl. Benzyl etc. are mentioned as aralkyl of the said aralkyl ester group. Examples of the ester group having a polymerizable double bond include 2-acryloyloxyethyl ester group and 2-methacryloyloxyethyl ester group.

Specific examples of the phosphoric acid ester include monoalkyl phosphates such as methyl phosphate; dialkyl phosphates such as dibutyl phosphate; Trimethylphosphate, Triethylphosphate, Tributylphosphate, Trioctylphosphate, Tridecylphosphate, Trioctadecylphosphate, Distearylpentaerythrityldiphosphate, Tris(2-chloroethyl)phosphate, Tris(2,3-dichloropropyl) ) trialkyl phosphates such as phosphate; tricycloalkyl phosphates such as tricyclohexyl phosphate; monoaryl phosphate; diaryl phosphate; triaryl phosphates such as triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, and 2-ethylphenyl diphenyl phosphate; 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, 3-methacryloyloxypropyl acid phosphate, methacryloyloxypolyoxyethylene glycol acid phosphate, methacryloyloxypolyoxy and phosphoric acid esters containing an ester group having a polymerizable double bond, such as propylene glycol acid phosphate.

Specific examples of the phosphonic acid include alkylphosphonic acids such as methylphosphonic acid and arylphosphonic acids such as phenylphosphonic acid.

Specific examples of the phosphinic acid include alkyl phosphinic acids such as methylphosphinic acid and arylphosphinic acids such as phenylphosphinic acid.

Especially, as said phosphoric acid ester, the phosphoric acid ester containing the ester group which has the said polymerizable double bond is preferable. When the phosphoric acid ester containing an ester group having a polymerizable double bond is used, when the curable resin composition containing the copolymer solution is cured, a cross-linked structure is formed with the copolymer or polymerizable compound, and the components included The volatilization and elution of is suppressed, and the occurrence of problems such as contamination of the reaction system and deterioration of electrical insulation can be remarkably suppressed.

It is preferable that the said phosphoric acid ester contains 2 or 3 or more polymerizable double bonds.

In the present invention, commercially available products can be used as phosphoric acid esters containing an ester group having a polymerizable double bond, for example, Light Ester P-1M, Light Ester P-2M (both manufactured by Kyoeisha Chemical), Phosphate Mer M (manufactured by Uni Chemical Co., Ltd.) and the like can be used. Especially, light ester P-2M is preferable.

It is preferable that it is 400 or less, and, as for the molecular weight of the said phosphoric acid derivative, it is more preferable that it is 350 or less. When the molecular weight of the phosphoric acid derivative is 400 or less, the resin solid content when added can be lowered, and the storage stability is further improved. In addition, the effect of improving the anionic property of acid groups and reducing the nucleophilic force becomes larger. It is preferable that it is 150 or more, and, as for the molecular weight of the said phosphoric acid derivative, it is more preferable that it is 250 or more. When the molecular weight of the phosphoric acid derivative is 150 or more, compatibility with the resin composition may be further improved.

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

The content of the acid compound and the phosphoric acid derivative is not particularly limited, and may be appropriately set according to the application or the blending of other components, but is preferably usually 0.01 to 5% by mass relative to 100% by mass of the total solid content of the copolymer solution. is preferable, 0.01 to 3 mass% is more preferable, and 0.02 to 2 mass% is still more preferable. In addition, the said content is the total amount of the said acid compound and a phosphoric acid derivative, when using the said acid compound and a phosphoric acid derivative together. In addition, in this specification, "the total amount of solid content" means the total amount of the components which form a hardened|cured material (excluding the solvent etc. which volatilized at the time of formation of a hardened|cured material).

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

When the copolymer solution further contains a basic compound described later, the content of the acid compound and the phosphoric acid derivative is preferably 50 to 200 mol% with respect to 100 mol% of the basic compound used, and 70 It is more preferable that it is -150 mol%, and it is still more preferable that it is 80-120 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 coloring of the cured product can be further suppressed. In addition, the said content is the total amount of the said acid compound and a phosphoric acid derivative, when using the said acid compound and a phosphoric acid derivative together.

<Basic compound>

The copolymer solution may further contain a basic compound. By including the basic compound, the crosslinking reaction proceeds satisfactorily even under low-temperature curing conditions of 160°C or lower during curing of the copolymer, and a cured product having even better solvent resistance can be provided.

As said basic compound, the above-mentioned basic compound is mentioned. Especially, an amine compound is preferable. Further, as the basic compound, secondary amines, tertiary amines, heterocyclic amines, and phosphorus compounds are more preferable in terms of ease of transpiration and ease of handling, and side reactions can be suppressed, and the molecular weight of the polymer after addition It is more preferable that it is a tertiary amine and a triphenylphosphine at the point which can suppress the raise of.

The content of the basic compound is not particularly limited, and may be appropriately set according to the use or the blending of other components, but is preferably 0.01 to 10% by mass, and preferably 0.01 to 6% with respect to 100% by mass of the total solid content of the copolymer solution. It is more preferable that it is mass %, and it is more preferable that it is 0.02-4 mass %.

The content of the basic compound is preferably from 0.01 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass, still more preferably from 0.1 to 6 parts by mass, based on 100 parts by mass of the copolymer.

In addition, when the basic compound used as a catalyst in the synthesis of the above-mentioned copolymer (at the time of addition reaction) remains in the copolymer solution after the synthesis of the copolymer, the basic compound is added according to the remaining amount to obtain the copolymer. What is necessary is just to adjust content in a solution.

<Method for producing copolymer solution>

As a method for producing the copolymer solution, for example, a step of polymerizing a monomer component containing an epoxy group-containing monomer represented by the formula (a) and a hydroxyl group-containing monomer represented by the formula (b1) (polymerization step) and a step of reacting the polymer obtained in the polymerization step with the acid group-containing compound represented by the formula (b2) or (b3) in the presence of a basic compound (reaction step), an acid compound having a pKa of 4.2 or less, and a protic polar solvent A method including a step of adding (adding step) is preferably used.

That is, the step of polymerizing the monomer component containing the epoxy group-containing monomer represented by formula (a) and the hydroxyl group-containing monomer represented by formula (b1), the polymer obtained in the polymerization step, and the formula (b2) or formula (b3) ) in the presence of a basic compound, and adding an acid compound having a pKa of 4.2 or less and a protic polar solvent. A method for producing a copolymer solution is also one of the present invention.

As the said polymerization process, the same process as the process (1) in the manufacturing method of the above-mentioned copolymer is mentioned.

As said reaction process, the method similar to the method of implementing the process (2) in the manufacturing method of the above-mentioned copolymer in presence of a basic compound is mentioned. Specific examples of the acid group-containing compound represented by the formula (b2) or formula (b3) and the basic compound include the same as the acid group-containing compound and basic compound described above.

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

3. Curable Resin Composition

The copolymer of the present invention and the copolymer solution can be used as a curable resin composition in combination with other components. Since the curable resin composition contains the copolymer of the present invention, a cured product having excellent solvent resistance can be provided even under low-temperature curing conditions. Moreover, when the said curable resin composition contains the said copolymer solution, it becomes what is also excellent also in storage stability. A curable resin composition containing the aforementioned copolymer or copolymer solution is also one of the preferred embodiments of the present invention.

In the curable resin composition, the content of the copolymer is not particularly limited, and may be appropriately set depending on the purpose of use or the blending of other components. It is preferably 10% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. do.

In addition, in this specification, "the total amount of solid content" means the total amount of the components which form a hardened|cured material (excluding the solvent etc. which volatilized at the time of formation of a hardened|cured material).

It is preferable that the said curable resin composition contains the above-mentioned protic polar solvent from the point which stability as a composition becomes favorable.

The content of the protic polar solvent in the curable resin composition is preferably 10% by mass or more, relative to 100% by mass of the solid content of the copolymer, from the viewpoint of ensuring the stability of the curable resin composition, 30% by mass or more It is more preferably 40% by mass or more, more preferably 3000% by mass or less, and more preferably 1000% by mass or less.

The content of the protic polar solvent in the curable resin composition is preferably 1 mass% or more, relative to 100 mass% of the solid content of the curable resin composition, from the point of ensuring the stability of the curable resin composition, 5 mass% or more It is more preferably 10% by mass or more, more preferably 400% by mass or less, more preferably 300% by mass or less, and still more preferably 200% by mass or less.

In addition, the curable resin composition may contain various components such as a polymerizable compound and a polymerization initiator. About various components, such as a polymeric compound and a polymerization initiator, the component etc. similar to the photosensitive resin composition mentioned later are mentioned.

As an example of a preferable aspect of the curable resin composition, a photosensitive resin composition will be described.

3-1. photosensitive resin composition

The copolymer of the present invention or the copolymer solution can be further used as a photosensitive resin composition by combining a polymerizable compound and a photopolymerization initiator.

Since the photosensitive resin composition contains the aforementioned copolymer, a cured product having excellent solvent resistance can be provided even under a low-temperature curing condition of 160°C or less, for example, about 90°C. In addition, since the polymeric compound is further included, a cured product excellent in various physical properties such as curability, adhesion to a substrate, surface hardness, and heat resistance can be provided. A photosensitive resin composition comprising the aforementioned copolymer or copolymer solution, a polymerizable compound, and a photopolymerization initiator is also one of the present inventions.

In the photosensitive resin composition of the present invention, the content of the copolymer is not particularly limited, and may be appropriately set depending on the use or the blending of other components. For example, based on 100% by mass of the total solid content of the photosensitive resin composition, It is preferably 5 mass% or more, more preferably 10 mass% or more, still more preferably 15 mass% or more, and preferably 80 mass% or less, more preferably 75 mass% or less, and 70 mass% or less more preferable

<polymerizable compound>

The polymerizable compound has a polymerizable unsaturated bond (also referred to as a polymerizable unsaturated group) that can be polymerized by irradiation of active energy rays such as free radicals, electromagnetic waves (eg, infrared rays, ultraviolet rays, X-rays, etc.), electron beams, etc. It is a low molecular weight compound having, for example, a monofunctional compound having one polymerizable unsaturated group in the molecule and a polyfunctional compound having two or more polymerizable unsaturated groups.

Examples of the monofunctional compound include N-substituted maleimide monomers; (meth)acrylic acid esters; (meth)acrylamides; unsaturated monocarboxylic acids; unsaturated polyhydric carboxylic acids; unsaturated monocarboxylic acids in which the chain between the unsaturated group and the carboxyl group is extended; unsaturated acid anhydrides; Aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates; etc. can be mentioned. As these, the thing same as the compound illustrated as a monomer component of the said copolymer is mentioned, for example. In addition, a monomer having 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, butylene glycol di(meth)acrylate, hexanedioldi Bifunctional (meth)acrylate compounds such as (meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, and bisphenol F alkylene oxide di(meth)acrylate ;

Trimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di Pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, ethylene oxide addition trimethylolpropane tri (meth)acrylate, ethylene oxide added ditrimethylolpropanetetra(meth)acrylate, ethylene oxide added pentaerythritol tetra(meth)acrylate, ethylene oxide added dipentaerythritol hexa(meth)acrylate, propylene oxide added Trimethylolpropane tri(meth)acrylate, propylene oxide added ditrimethylolpropanetetra(meth)acrylate, propylene oxide added pentaerythritol tetra(meth)acrylate, propylene oxide added dipentaerythritol hexa(meth)acrylate , ε-caprolactone addition trimethylolpropane tri(meth)acrylate, ε-caprolactone addition ditrimethylolpropanetetra(meth)acrylate, ε-caprolactone addition pentaerythritol tetra(meth)acrylate, ε-capro Lactone added dipentaerythritol hexa(meth)acrylate, dipentaerythritol pentaacrylate succinic acid modified product, pentaerythritol triacrylate succinic acid modified product, dipentaerythritol pentaacrylate phthalic acid modified product, pentaerythritol triacrylic acid Late phthalic acid modified product, formula:

[Formula 24]

Polyfunctional (meth)acrylate compounds of tri- or higher functionality, such as modified substances of dipentaerythritol hexaacrylate represented by;

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkyl Rene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene polyfunctional vinyl ethers such as oxide-added trimethylol-propane trivinyl ether, ethylene oxide-added ditrimethylol-propane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexavinyl ether;

(meth)acrylate 2-vinyloxyethyl, (meth)acrylate 3-vinyloxypropyl, (meth)acrylate 1-methyl-2-vinyloxyethyl, (meth)acrylate 2-vinyloxypropyl, (meth)acrylate 4- Vinyloxybutyl, (meth)acrylate 4-vinyloxycyclohexyl, (meth)acrylate 5-vinyloxypentyl, (meth)acrylate 6-vinyloxyhexyl, (meth)acrylate 4-vinyloxymethylcyclohexylmethyl, (meth)acrylate (meth)acrylic acid containing vinyl ether groups such as p-vinyloxymethylphenylmethyl acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylic acid, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylic acid esters;

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkyl Renoxide diallyl ether, trimethylolpropanetriallyl ether, ditrimethylolpropanetetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene polyfunctional allyl ethers such as oxide-added trimethylolpropanetriallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, and ethylene oxide-added dipentaerythritol hexaallyl ether;

allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate; Tri(acryloyloxyethyl) isocyanurate, tri(methacryloyloxyethyl) isocyanurate, alkylene oxide addition tri(acryloyloxyethyl) isocyanurate, alkylene oxide addition tri( polyfunctional (meth)acryloyl group-containing isocyanurates such as methacryloyloxyethyl)isocyanurate; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; Reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate Polyfunctional urethane (meth)acrylates obtained by; polyfunctional aromatic vinyls such as divinylbenzene; etc. These polymeric compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

However, since the polymer which has a vinyl ether group in a side chain improves the curability of a resin composition, but may reduce storage stability, the said photosensitive resin composition has a polymer which has a vinyl ether group in a side chain from the point of storage stability. It is preferable not to include

Among the above polymerizable compounds, it is preferable to use a polyfunctional polymerizable compound from the viewpoint of further enhancing the curability of the photosensitive resin composition. As a functional number of the said polyfunctional polymeric 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 a molecular weight of the said polymeric compound, For example, 2000 or less is preferable from a handling viewpoint.

Among the above polyfunctional polymerizable compounds, from the viewpoints of reactivity, economy, availability, etc., preferably polyfunctional (meth)acrylate compounds, polyfunctional urethane (meth)acrylate compounds, and (meth)acrylic compounds are preferred. Compounds having a (meth)acryloyl group, such as isocyanurate compounds containing a loyl group, are exemplified, and polyfunctional (meth)acrylate compounds are more preferred. By containing the compound which has a (meth)acryloyl group, the photosensitive resin composition becomes a thing more excellent in photosensitivity and sclerosis|hardenability, and the hardened|cured material of still higher hardness and high transparency can be obtained. As the polyfunctional polymerizable compound, it is more preferable to use a trifunctional or higher polyfunctional (meth)acrylate compound.

As for the said polymeric compound, only 1 type may be used, and may be used in combination of 2 or more types.

In the photosensitive resin composition of the present invention, the content of the polymerizable compound is not particularly limited as long as the effect of the present invention is exhibited, and may be appropriately set. It is preferably 5 to 60% by mass, more preferably 10 to 50% by mass with respect to 100% by mass of the total solid content of the composition.

<Photoinitiator>

As the photopolymerization initiator, a radically polymerizable photopolymerization initiator is preferably used. A radically polymerizable photopolymerization initiator generates polymerization initiating radicals by irradiation with active energy rays such as electromagnetic waves and electron beams.

Specific examples of the photopolymerization initiator include, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("IRGACURE907", manufactured by BASF), 2 -Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 ("IRGACURE369", manufactured by BASF), 2-dimethylamino-2-(4-methyl-benzyl)-1- amino ketone compounds such as (4-morpholin-4-yl-phenyl)-butan-1-one ("IRGACURE379", manufactured by BASF); Benzyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one ("IRGACURE651", manufactured by BASF) and phenylglyoxylic acid methyl ester ("DAROCUR MBF", manufactured by BASF) compound; 1-hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE184", manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one ("DAROCUR1173", manufactured by BASF), 1 -[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one ("IRGACURE2959", manufactured by BASF), 2-hydroxy-1-{ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one ("IRGACURE127", manufactured by BASF), [1-hydroxy- cyclohexyl-phenyl-ketone + benzophenone] ("IRGACURE500", manufactured by BASF) and other hydroketone-based compounds; In addition to the like, other alkylphenone compounds exemplified in Unexamined-Japanese-Patent No. 2013-227485, paragraphs [0084] to [0086]; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime) ("OXE01", manufactured by BASF), ethanone, 1-[9-ethyl-6- (2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) ("OXE02", manufactured by BASF), 1,2-octanedione, 1-[4-(phenyl Thio)-,2-,(O-benzoyloxime)], ethanone ("OXE03", manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- oxime ester compounds such as yl]-,1-(O-acetyl oxime) ("OXE04", manufactured by BASF); benzophenone-based compounds; benzoin-based compounds; thioxanthone-based compounds; halomethylated triazine-based compounds; halomethylated oxadiazole-based compounds; Biimidazole type compounds; titanocene-based compounds; benzoic acid ester compounds; acridine-based compounds, etc.; phosphine oxide compounds; etc. can be mentioned. Especially, an amino ketone type compound and an oxime ester type compound are preferable.

The said photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the photopolymerization initiator is not particularly limited as long as the effect of the present invention is exhibited, and may be appropriately set. It is preferably %, more preferably 0.5 to 10% by mass, and still more preferably 1 to 8% by mass.

<mine generator>

It is preferable that the photosensitive resin composition of this invention contains a photo-acid generator further. By further including a photoacid generator, the curability of the photosensitive resin composition can be further improved.

The photoacid generator is a compound that generates an acid when exposed to active energy rays such as radiation. For example, strong acids such as toluenesulfonic acid or boron tetrafluoride, sulfonium salts, ammonium salts, phosphonium salts, iodonium salts, or selenium onium salts such as salt; iron-allene complexes; silanol-metal chelate complexes; sulfonic acid derivatives such as disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imide sulfonates, and benzoin sulfonates; organic halogen compounds; etc. can be mentioned.

The content of the photoacid generator is preferably from 0.3 to 20% by mass, more preferably from 0.5 to 10% by mass, still more preferably from 1 to 8% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition. do.

＜Other ingredients＞

The photosensitive resin composition of this invention may contain other components as needed other than the component mentioned above. As said other component, it is a solvent, for example; colorants (pigments, dyes); dispersant; heat resistance improver; leveling agent; development aids; inorganic fine particles such as silica fine particles; Coupling agents, such as a silane system, an aluminum system, and a titanium system; Thermosetting resins, such as a filler, an epoxy resin, a phenol resin, and polyvinyl phenol; curing aids such as polyfunctional thiol compounds; plasticizer; Polymerization inhibitor; ultraviolet absorbers; antioxidant; gloss remover; antifoaming agent; antistatic agent; slip agent; surface modifier; thixotropic agents; thixotropic adjuvants; quinonediazide compounds; polyhydric phenol compounds; Cationic polymerizable compound; acid generator; etc. can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type. These other components may be appropriately selected and used from known ones, and their amount can also 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 color 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 each of the above-described components using various mixers or dispersers can be heard The mixing/dispersion step is not particularly limited, and may be performed by a known method. Moreover, you may further include other normally performed processes. When the photosensitive resin composition contains a color material, it is preferably prepared through a known process such as a color material dispersion treatment process.

<cured material>

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

When the cured product is a cured film, the film thickness is preferably 0.1 μm or more. When the film thickness is 0.1 µm or more, even better solvent resistance can be exhibited. As for the said film thickness, it is more preferable that it is 0.5 micrometer or more, and it is still more preferable that it is 1 micrometer or more. The upper limit of the film thickness is not particularly limited, and may be appropriately set depending on the purpose and use of the cured film. For example, it is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less.

The method for obtaining the cured product is not particularly limited, and a known method may be used. For example, the above-described copolymer, copolymer solution, or photosensitive resin composition is applied to a substrate or molded. A method of obtaining a cured product by curing the cured product by drying, heating, irradiation of energy rays such as ultraviolet rays, or a combination thereof is exemplified.

When the copolymer, copolymer solution, or photosensitive resin composition of the present invention is used, a cured product having excellent solvent resistance can be provided even under low-temperature curing conditions. As a method for producing such a cured product, for example, a step of applying the photosensitive resin composition on a substrate to form a coating film, a step of irradiating the formed coating film with light, and a temperature of 160 ° C. or less for the light-irradiated coating film. A method including a step of heating in is preferably mentioned.

The substrate is not particularly limited, and may be appropriately selected according to the purpose or use, and examples thereof include substrates made of various materials such as a glass plate and a plastic plate.

A method of forming a coated film by applying the photosensitive resin composition is not particularly limited, and a known method such as spin coating, slit coating, roll coating, or cast coating can be used.

In the above production method, it is preferable to apply the photosensitive resin composition on a substrate and then dry the coating to form a coating film. The drying can be performed by a known method, and specifically, can be performed by the same method as the drying method described in "Batch Step" of "<Color Filter Manufacturing Method>" described later.

The manufacturing method includes a step of irradiating the coating film with light after forming the coating film.

The method of irradiating the formed coating film with light is not particularly limited, and can be carried out by a known method. Specifically, the method described in “Light Irradiation Step” of “Method for Manufacturing Color Filter” to be described later. can be carried out in the same way as

When irradiating light to the said coating film, you may light-irradiate through a photomask. As the photomask, a mask in which a light-shielding portion is formed according to a target pattern may be used. When light irradiation is performed through a photomask, it is preferable to perform a developing process after that. By performing the image development process, a target pattern can be formed on the coated film. The developing method is not particularly limited, and can be carried out by a known method. Specifically, it can be carried out by the same method as the method described in "Development Step" of "<Color Filter Manufacturing Method>" described later. .

The manufacturing method also includes a step of heating the light-irradiated coating film to 160°C or lower. Since the said manufacturing method uses the photosensitive resin composition mentioned above, the heating process (post-curing process) after light irradiation can be performed on comparatively low-temperature conditions like 160 degreeC or less.

It is preferable that it is 155 degrees C or less, and, as for heating temperature, it is more preferable that it is 150 degrees C or less. The lower limit of the heating temperature is preferably 70°C or higher, and more preferably 90°C or higher, from the viewpoint of maintaining curability.

The heating method other than the temperature is not particularly limited, and can be carried out by a known method. For example, by the same method as described in "Heating Step" of "<Color Filter Manufacturing Method>" described later. can be carried out.

<Use>

The copolymer of the present invention, the copolymer solution, and the photosensitive resin composition (curable resin composition) containing the copolymer sufficiently undergo a curing reaction even under low-temperature curing conditions of 160 ° C. or less, for example, about 90 ° C., and thus have excellent solvent resistance. Excellent cured products can be provided. Therefore, it can be suitably used for applications requiring sufficient curing under low-temperature conditions or applications requiring solvent resistance.

The copolymer, copolymer solution, and photosensitive resin composition of the present invention are specifically, for example, used for liquid crystal/organic EL/quantum dot/micro LED liquid crystal display devices, solid-state imaging devices, touch panel display devices, etc. Suitable for use in various optical members such as color filters, black matrices, photo spacers, black column spacers, inks, printed boards, printed wiring boards, semiconductor elements, photoresists, insulating films, films, organic protective films, and constituent members of electric/electronic devices. can be used Among them, it is preferably used for color filter applications.

The photosensitive resin composition of the present invention is preferably used for optical materials, and is also preferably used for negative types.

3. Color filter

A color filter having a cured product of the photosensitive resin composition described above on a substrate is also one of the preferred embodiments of the present invention.

In the color filter, the cured product formed from the photosensitive resin composition described above is particularly preferable as a segment requiring coloring such as a black matrix or each pixel such as red, green, blue, and yellow, for example. It is also suitable as a segment that does not necessarily require coloring of a photo spacer, a protective layer, a rib for orientation control, or the like.

Examples of the substrate used for the color filter include glass substrates such as white plate glass, blue plate glass, alkali tempered glass, and silica-coated blue plate glass; Sheets, films, or substrates made of thermoplastic resins such as polyester, polycarbonate, polyolefin, polysulfone, ring-opening polymers of cyclic olefins, and hydrogenated products thereof; Sheets, films or substrates made of thermosetting resins such as epoxy resins and unsaturated polyester resins; Metal substrates, such as an aluminum plate, a copper plate, a nickel plate, and a stainless steel plate; ceramic substrate; semiconductor substrates having photoelectric conversion elements; Members composed of various materials such as a glass substrate having a color material layer on the surface (for example, a color filter for LCD); etc. can be mentioned. Among them, from the viewpoint of heat resistance, a glass substrate or a sheet, film or substrate made of a heat-resistant resin is preferable. In addition, it is preferable that the said substrate is a transparent substrate.

Further, the substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment using a silane coupling agent, or the like, if necessary.

<Production method of color filter>

In order to obtain the color filter, for example, a step of disposing the above-described photosensitive resin composition on a substrate per pixel (that is, per pixel of one color) (also referred to as a disposition step), and on the substrate A method including a step of irradiating light to the placed photosensitive resin composition (also referred to as a light irradiation step), a step of developing with a developing solution (also referred to as a developing step), and a step of heat treatment (also referred to as a heating step) It is preferable to adopt a manufacturing method in which the same method is employed and repeated for each color. In addition, the formation order of each color pixel is not specifically limited.

(1) Placement process (preferably application process)

It is preferable to perform the said batching process by application|coating. As a method of applying the photosensitive resin composition on a substrate, for example, spin coating, slit coating, roll coating, casting coating, etc. can be used, and any method can be used preferably.

In the arrangement step, it is preferable to dry the coating film after applying the photosensitive resin composition on the substrate. Drying of the coating film can be performed using, for example, a hot plate, an IR oven, a convection oven or the like. Drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of curing component, the film thickness, and the performance of the dryer, but it is usually preferably carried out at a temperature of 50 to 160 ° C. for 10 seconds to 300 seconds.

(2) Light irradiation process

In the light irradiation step, as the light source of the actinic light used, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp Laser light sources such as lamp light sources, argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, semiconductor lasers, etc. are used. Moreover, although a proximity system, a mirror projection system, and a stepper system are mentioned as a system of an exposure machine, a proximity system is used preferably.

In addition, in the irradiation step of an active energy ray, it is good also as irradiating an active energy ray through a predetermined mask pattern depending on a use. In this case, the exposed portion is cured, and the cured portion becomes insoluble or poorly soluble in the developing solution.

(3) Development process

The said developing process is a process of carrying out the development process with a developing solution after the above-mentioned light irradiation process, and removing an unexposed part and forming a pattern. In this way, a patterned cured film can be obtained. The development treatment can be usually carried out at a developing temperature of 10 to 50°C by methods such as immersion development, spray development, brush development, and ultrasonic development.

The developing solution used in the developing step is not particularly limited as long as it dissolves the photosensitive resin composition, but usually an organic solvent or an alkaline aqueous solution is used, and a mixture thereof may be used. Moreover, when using alkaline aqueous solution as a developing solution, it is preferable to wash|clean with water after image development. Examples of the organic solvent and alkaline aqueous solution include the same ones as those described in Unexamined-Japanese-Patent No. 2015-157909.

(4) heating process

The said heating process is a process (it is also called a "post-curing process") of further hardening an exposed part (hardening part) by baking after the above-mentioned image development process. For example, a step of post-exposure using a light source such as a high-pressure mercury lamp with a light amount of 0.5 to 5 J/cm 2 , a step of post-heating at a temperature of, for example, 60 to 200° C. for 10 seconds to 120 minutes, etc. can be heard By performing such a post-curing step, it becomes possible to further strengthen the hardness and adhesion of the patterned cured film.

The heating step is generally performed at a temperature of about 200 to 260 ° C., but when the photosensitive resin composition is used, sufficient curing can be performed under relatively low conditions of 200 ° C. or less, preferably 160 ° C. or less. there is. Therefore, a product having excellent solvent resistance can be obtained without impairing the properties maintained by the substrate or the cured product.

In the 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. Moreover, 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, It is preferable to set it as 5 to 60 minutes, for example. Also, the heating method is not particularly limited, but it can be carried out using, for example, a heating device such as a hot plate, a convection oven, or a high-frequency heater.

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

4. Display device

The display device provided with the above-mentioned color filter is also one of the preferable aspects in this invention.

A member for a display device and a display device having a cured product of the photosensitive resin composition are also included in preferred embodiments of the present invention. A cured product (cured film) formed from the photosensitive resin composition is stable, has excellent adhesion to substrates, etc., is highly rigid, exhibits high smoothness, and has a high transmittance, so it is particularly preferable as a transparent member. It is also useful as a protective film or insulating film in various display devices.

As said display device, a liquid crystal display device, a solid-state image sensor, a touch-panel type display device etc. are preferable, for example.

In addition, when using the said cured product (cured film) as a member for display devices, the said member may be a film-like single-layer or multi-layered member comprised from the said cured film, and another layer in addition to the said single-layer or multi-layered member. This combined member may be sufficient, and the member which contains the said cured film in a structure may be sufficient.

As described above, the copolymer, copolymer solution, and photosensitive resin composition (curable resin composition) of the present invention can provide a cured product having excellent solvent resistance even under low-temperature curing conditions. The copolymer, the copolymer solution, and the photosensitive resin composition of the present invention are used as various optical members and constituent members for liquid crystal/organic EL/quantum dot/micro LED liquid crystal display devices, solid-state imaging devices, touch panel display devices, etc. · It can be used suitably for various uses, such as an electronic device.

Example

The present invention will be described in more detail by way of examples below, but the present invention is not limited only to these examples. In addition, "part" shall mean "mass part" and "%" shall mean "mass %" unless there is particular notice.

In this Example, the measurement of various physical properties and the like was carried out by the following method.

(1) weight average molecular weight (Mw)

Using polystyrene as a standard substance and tetrahydrofuran as an eluent, the weight average molecular weight was determined by the GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh Corporation) and column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation). measured.

(2) solid content

About 1 g of the copolymer solution was weighed and placed in an aluminum cup, dissolved by adding about 3 g of acetone, and then naturally dried at room temperature. Then, after drying at 140°C for 1.5 hours under a vacuum using a hot air dryer (trade name: PHH-101, manufactured by Espec Co., Ltd.), 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 amount.

(3) acid value

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

(4) Epoxy equivalent (g/equivalent)

It was determined by dividing the mass (g) of the solid content of the copolymer by the number of moles (mol) of epoxy groups contained in the copolymer.

(5) Double bond equivalent weight (g/equivalent)

It was determined by dividing the mass (g) of the solid content of the copolymer by the amount (mol) of double bonds in 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 heated at 90 ° C. or 110 ° C. for 40 minutes, respectively. Treatment (post-curing) was performed to obtain a cured film having a film thickness of 2 μm. Then, 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 with respect to the immersion liquid (NMP) after taking out the cured film, spectrophotometer UV3100 (manufactured by Shimadzu Corporation) ), and the absorbance was measured, and evaluated according to the following criteria. A larger value of the absorbance indicates that a lot of the colorant is eluted in the immersion liquid, and the photosensitive resin composition is evaluated as having low solvent resistance.

(Evaluation standard)

◎: The absorbance value is less than 0.2

○: The absorbance value is 0.2 or more and less than 0.3

△: Absorbance value of 0.3 or more and less than 0.4

×: The absorbance value is 0.4 or more

XX: film peeling

(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 subjected to heat treatment (post-curing) at 90°C for 30 minutes. This was carried out to obtain a cured film having a thickness of 2 μm. Then, the cured film was immersed in 20 g of the immersion solvent shown in Table 5 at 30° C. for 5 minutes, then taken out, and the absorbance was measured for the immersion solvent after taking out the cured film with a spectrophotometer UV3100 (manufactured by Shimadzu Corporation).

(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) Remaining Film Rate

The residual film rate was calculated by measuring the weight of the film before and after the evaluation of 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. After that, the remaining film rate was calculated by dividing the film weight after solvent resistance evaluation by the film weight before evaluation.

(Production Example 1)

Preparation of copolymer solution A-1 (SAH adduct solution of HEMA-GMA copolymer)

185.3 parts of propylene glycol monomethyl ether acetate were introduced into a reaction tank equipped with a thermometer, stirrer, gas inlet pipe, cooling pipe, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90 degreeC. On the other hand, as a dropping tank (A), 30.0 parts of 2-hydroxyethyl methacrylate, 70.0 parts of glycidyl methacrylate, 30 parts of propylene glycol monomethyl ether acetate, t-butylperoxy-2-ethylhexa in a beaker A mixture of 2.0 parts of Noate ("Perbutyl (registered trademark) O" manufactured by Nihon Oil Co., Ltd.) was stirred and mixed, and 2.0 parts of n-dodecylmercaptan and 18.0 parts of propylene glycol monomethyl ether acetate were added to the dropping tank (B). Stirring and mixing were prepared. After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, 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 to obtain copolymer solution A got -1 Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 2)

Preparation of copolymer solution A-2 (solution of SAH adduct of BzMI-CHMA-HEMA-GMA copolymer)

172.0 parts of propylene glycol monomethyl ether acetate were introduced into a reaction vessel equipped with a thermometer, stirrer, gas inlet tube, cooling tube, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90°C. On the other hand, as the dropping tank (A), in a beaker, 10.0 parts of N-benzylmaleimide, 43.6 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 16.4 parts of glycidyl methacrylate, and propylene glycol mono A mixture of 30 parts of methyl ether acetate and 2.0 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl (registered trademark) O" manufactured by Japan Oil Co., Ltd.) was prepared, and in the dropping tank (B), n - Prepared by stirring and mixing 2.0 parts of dodecylmercaptan and 31.33 parts of propylene glycol monomethyl ether acetate. After the temperature of the reaction tank reached 90°C, while maintaining the same temperature, dripping was started from the dropping tank over 3 hours to perform polymerization. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes. Then, after cooling to room temperature, it was made to react with 11.5 parts of succinic anhydride, 0.33 part of triethylamine as a catalyst, and 29.0 parts of propylene glycol monomethyl ether acetate at 60 degreeC for 10 hours, and copolymer solution A-2 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 3)

Preparation of copolymer solution A-3 (solution of SAH adduct of BzMI-VT-HEMA-GMA copolymer)

172.0 parts of propylene glycol monomethyl ether acetate were introduced into a reaction vessel equipped with a thermometer, stirrer, gas inlet tube, cooling tube, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90°C. On the other hand, as the dropping tank (A), 10.0 parts of N-benzylmaleimide, 43.6 parts of vinyltoluene, 30.0 parts of 2-hydroxyethyl methacrylate, 16.4 parts of glycidyl methacrylate, and propylene glycol monomethyl ether acetate were added to a beaker. A mixture of 30 parts and 2.0 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl (registered trademark) O” manufactured by Japan Oil Co., Ltd.) was prepared, and in the dropping tank (B), n-dodecyl A stirring mixture of 2.0 parts of mercaptan and 31.33 parts of propylene glycol monomethyl ether acetate was prepared. After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes. Then, after cooling to room temperature, it was made to react with 11.5 parts of succinic anhydride, 0.33 part of triethylamine as a catalyst, and 29.0 parts of propylene glycol monomethyl ether acetate at 60 degreeC for 10 hours, and copolymer solution A-3 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 4)

Preparation of copolymer solution A-4 (solution of SAH adduct of BzMI-2EHA-HEMA-GMA copolymer)

172.0 parts of propylene glycol monomethyl ether acetate were introduced into a reaction vessel equipped with a thermometer, stirrer, gas inlet tube, cooling tube, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90°C. On the other hand, as the dropping tank (A), 10.0 parts of N-benzylmaleimide, 43.6 parts of 2-ethylhexyl acrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 16.4 parts of glycidyl methacrylate, and propylene glycol were added to a beaker. A mixture of 30 parts of monomethyl ether acetate and 2.0 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl (registered trademark) O" manufactured by Nippon Oil Co., Ltd.) was prepared, and in the dropping tank (B), A stirring mixture of 2.0 parts of n-dodecylmercaptan and 31.33 parts of propylene glycol monomethyl ether acetate was prepared. After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes. Then, after cooling to room temperature, it was made to react with 11.5 parts of succinic anhydride, 0.33 part of triethylamine as a catalyst, and 29.0 parts of propylene glycol monomethyl ether acetate at 60 degreeC for 10 hours, and copolymer solution A-4 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 5)

Preparation of copolymer solution A-5 (solution of SAH adduct of BzMI-CHMA-HEAA-GMA copolymer)

85.6 parts of diethylene glycol ethyl methyl ether was introduced into a reaction tank equipped with a thermometer, stirrer, gas inlet pipe, cooling pipe, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90 degreeC. On the other hand, as the dropping tank (A), 10.0 parts of N-benzylmaleimide, 46.65 parts of cyclohexyl methacrylate, 26.8 parts of N-hydroxyethyl acrylamide, 16.55 parts of glycidyl methacrylate, and diethylene glycol ethyl were added to a beaker. A mixture of 49.8 parts of methyl ether and 2.0 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl (registered trademark) O” manufactured by Nihon Oil Co., Ltd.) was prepared, and in the dropping tank (B), n- 2.0 parts of dodecyl mercaptan and 98.0 parts of diethylene glycol ethyl methyl ether were stirred and mixed to prepare. After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes. Then, after cooling to room temperature, 13.0 parts of succinic anhydride and 32.5 parts of diethylene glycol ethyl methyl ether were made to react at 60 degreeC for 10 hours, and copolymer solution A-5 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 6)

Preparation of copolymer solution A-6 (solution of SAH adduct of BzMI-CHMA-GLMA-GMA copolymer)

50.1 parts of propylene glycol monomethyl ether acetate and 50.1 parts of diethylene glycol ethyl methyl ether were introduced into a reaction tank equipped with a thermometer, stirrer, gas inlet pipe, cooling pipe, and dropping tank inlet, and after nitrogen substitution, heating to 90 ° C. heated up to On the other hand, as the dropping tank (A), in a beaker, 10.0 parts of N-benzylmaleimide, 46.65 parts of cyclohexyl methacrylate, 30.0 parts of glycerin monomethacrylate ("Blemmer GL" manufactured by Nihon Yuji Co., Ltd.), glyceryl methacrylate 13.35 parts of cydyl, 24.1 parts of propylene glycol monomethyl ether acetate, 24.1 parts of diethylene glycol ethyl methyl ether, t-butylperoxy-2-ethylhexanoate ("Perbutyl (registered trademark) O" manufactured by Nippon Yuji Co., Ltd.) What stirred and mixed 2.0 parts was prepared, and what stirred and mixed 2.0 parts of n-dodecyl mercaptan, 42.5 parts of propylene glycol monomethyl ether acetate, and 42.5 parts of diethylene glycol ethylmethyl ether was prepared in the dropping tank (B). After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, 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 ethylmethyl ether were reacted at 60°C for 10 hours to obtain copolymer solution A-6. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 7)

Preparation of copolymer solution A-7 (solution of SAH adduct of BzMI-CHMA-HEMA-GMA-NIPAM copolymer)

30.9 parts of propylene glycol monomethyl ether acetate was introduced into a reaction tank equipped with a thermometer, stirrer, gas inlet pipe, cooling pipe, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90 degreeC. On the other hand, as the dropping tank (A), in a beaker, 10.0 parts of N-benzylmaleimide, 23.6 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 16.4 parts of glycidyl methacrylate, and N-iso 20.0 parts of propyl acrylamide, 10.0 parts of propylene glycol monomethyl ether acetate, and 2.0 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl (registered trademark) O” manufactured by Nippon Oil Co., Ltd.) were stirred and mixed to prepare , What stirred and mixed 4.0 parts of n-dodecyl mercaptan and 67.4 parts of propylene glycol monomethyl ether acetate was prepared in the dropping tank (B). After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes. Then, after cooling to room temperature, 11.5 parts of succinic anhydride and 4.7 parts of propylene glycol monomethyl ether acetate were made to react at 60 degreeC for 10 hours, and copolymer solution A-7 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 8)

Preparation of copolymer solution A-8 (solution of SAH adduct of MAA adduct of BzMI-CHMA-HEMA-GMA copolymer)

64.0 parts of propylene glycol monomethyl ether acetate were introduced into a reaction vessel equipped with a thermometer, stirrer, gas inlet tube, cooling tube, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90°C. On the other hand, as a dropping tank (A), in a beaker, 10.0 parts of N-benzylmaleimide, 19.0 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 41.0 parts of glycidyl methacrylate, and propylene glycol mono A mixture of 10.0 parts of methyl ether acetate and 2.0 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl (registered trademark) O" manufactured by Japan Oil Co., Ltd.) was prepared, and in the dropping tank (B), n - Prepared by stirring and mixing 4.0 parts of dodecylmercaptan and 54.82 parts of propylene glycol monomethyl ether acetate. After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes. Then, after cooling to room temperature, 13.5 parts of methacrylic acid and 0.34 part of triphenylphosphine as a catalyst and 0.17 part of Antage W-400 were reacted at 85°C for 12 hours. Then, after cooling to room temperature, 13.1 parts of succinic anhydride was made to react at 60 degreeC for 5 hours, and copolymer solution A-8 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 9)

Preparation of copolymer solution A-9 (solution of SAH adduct of Karenz MOI adduct of BzMI-CHMA-HEMA-GMA copolymer)

208.7 parts of propylene glycol monomethyl ether acetate were introduced into a reaction tank equipped with a thermometer, stirrer, gas inlet pipe, cooling pipe, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90 degreeC. On the other hand, as the dropping tank (A), in a beaker, 10.0 parts of N-benzylmaleimide, 14.3 parts of cyclohexyl methacrylate, 55.0 parts of 2-hydroxyethyl methacrylate, 20.7 parts of glycidyl methacrylate, and propylene glycol mono A mixture of 10.0 parts of methyl ether acetate and 2.0 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl (registered trademark) O" manufactured by Japan Oil Co., Ltd.) was prepared, and in the dropping tank (B), n - Prepared by stirring and mixing 2.0 parts of dodecylmercaptan and 98.00 parts of propylene glycol monomethyl ether acetate. After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes. Then, after cooling to room temperature, 2-isocyanatoethyl methacrylate (“Karenz MOI (registered trademark)” manufactured by Showa Denko) 26.2 parts, triethylamine 0.13 parts, 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 part of triethylamine as a catalyst were reacted at 60°C for 7 hours, and further 69 parts of propylene glycol monomethyl ether were added and reacted at 60°C for 1 hour to obtain the remaining Succinic anhydride was lost to obtain copolymer solution A-9. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 10)

Preparation of copolymer solution A-10 (SAH adduct solution of AMA-TBMA-HEMA-GMA copolymer)

172 parts of propylene glycol monomethyl ether acetate were introduced into a reaction tank equipped with a thermometer, stirrer, gas inlet pipe, cooling pipe, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90 degreeC. On the other hand, as the dropping tank (A), 10.0 parts of α-(allyloxymethyl)methyl acrylate, 43.6 parts of tert-butyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, and 16.4 parts of glycidyl methacrylate were added to a beaker. , 30.0 parts of propylene glycol monomethyl ether acetate and 2.0 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl (registered trademark) O” manufactured by Nihon Oil Co., Ltd.) were stirred and mixed to prepare a dropping tank (B ), prepared by stirring and mixing 2.0 parts of n-dodecylmercaptan and 31.3 parts of propylene glycol monomethyl ether acetate. After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes. Then, after cooling to room temperature, 11.5 parts of succinic anhydride, 0.33 part of triethylamine as a catalyst, and 29.04 parts of propylene glycol monomethyl ether acetate were made to react at 60 degreeC for 10 hours, and copolymer solution A-10 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 11)

Preparation of copolymer solution A-11 (solution of SAH adduct of AA adduct of MD-CHMA-HEMA-GMA copolymer)

86.5 parts of propylene glycol monomethyl ether acetate were introduced into a reaction tank equipped with a thermometer, stirrer, gas inlet pipe, cooling pipe, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90 degreeC. On the other hand, as the dropping tank (A), 10.0 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 43.6 parts of cyclohexyl methacrylate, and 2-hydroxy methacrylate were added to a beaker. 30.0 parts of ethyl, 16.4 parts of glycidyl methacrylate, 48.8 parts of propylene glycol monomethyl ether acetate, t-butylperoxy-2-ethylhexanoate (“Perbutyl (registered trademark) O” manufactured by Nippon Oil Co., Ltd.) 2.0 What stirred and mixed part was prepared, and what stirred-mixed 2.0 parts of n-dodecyl mercaptan and 98 parts of propylene glycol monomethyl ether acetate was prepared in the dropping tank (B). After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes. Then, after cooling to room temperature, 5.0 parts of acrylic acid, 0.32 part of triethylamine as a catalyst, 0.16 part 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 anhydride and 20 parts of propylene glycol monomethyl ether acetate were made to react at 60 degreeC for 10 hours, and the copolymer solution A-11 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 12)

Preparation of copolymer solution A-12 (SAH adduct solution of CHMI-CHMA-HEMA-GMA copolymer)

172 parts of propylene glycol monomethyl ether acetate were introduced into a reaction tank equipped with a thermometer, stirrer, gas inlet pipe, cooling pipe, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90 degreeC. On the other hand, as a dripping tank (A), 10.0 parts of N-cyclohexylmaleimide, 43.6 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 16.4 parts of glycidyl methacrylate, and propylene glycol were added to a beaker. A mixture of 30.0 parts of monomethyl ether acetate and 2.0 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl (registered trademark) O" manufactured by Japan Oil Co., Ltd.) was prepared, and in the dropping tank (B), A stirring mixture of 2.0 parts of n-dodecylmercaptan and 31.3 parts of propylene glycol monomethyl ether acetate was prepared. After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes. Then, after cooling to room temperature, 11.5 parts of succinic anhydride, 0.33 part 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 copolymer solution A-12. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 13)

Preparation of copolymer solution A-13 (solution of SAH adduct of BzMI-DCPMA-HEMA-GMA copolymer)

53.4 parts of propylene glycol monomethyl ether acetate were introduced into a reaction tank equipped with a thermometer, stirrer, gas inlet pipe, cooling pipe, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90 degreeC. On the other hand, as the dropping tank (A), in a beaker, 5.0 parts of N-benzylmaleimide, 25.0 parts of dicyclopentanyl methacrylate, 40.0 parts of 2-hydroxyethyl methacrylate, 30.0 parts of glycidyl methacrylate, and propylene glycol mono A mixture of 10 parts of methyl ether acetate and 2.0 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl (registered trademark) O” manufactured by Nihon Oil Co., Ltd.) was prepared, and in the dropping tank (B), n - Prepared by stirring and mixing 6.0 parts of dodecylmercaptan and 54.0 parts of propylene glycol monomethyl ether acetate. After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes. Then, after cooling to room temperature, after reacting 23.1 parts of succinic anhydride, 9.13 parts of propylene glycol monomethyl ether acetate, and 60°C for 12 hours, dilution was performed with 172 parts of propylene glycol monomethyl ether. Copolymer solution A-13 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 14)

Preparation of copolymer solution A-14 (solution of SAH adduct of BzMI-CHMA-HEMA-GMA copolymer)

165.3 parts of propylene glycol monomethyl ether acetate were introduced into a reaction tank equipped with a thermometer, stirrer, gas inlet pipe, cooling pipe, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90 degreeC. On the other hand, as the dropping tank (A), in a beaker, 10.0 parts of N-benzylmaleimide, 27.5 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 32.5 parts of glycidyl methacrylate, and propylene glycol mono A mixture of 30 parts of methyl ether acetate and 2.0 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl (registered trademark) O" manufactured by Japan Oil Co., Ltd.) was prepared, and in the dropping tank (B), n - Prepared by stirring and mixing 2.0 parts of dodecylmercaptan and 38.0 parts of propylene glycol monomethyl ether acetate. After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes. 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, followed by dilution with 76 parts of propylene glycol monomethyl ether. did A copolymer solution A-14 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 15)

Preparation of copolymer solution A-15 (solution of SAH adduct of BzMI-2EHA-HEMA-GMA copolymer)

172.0 parts of propylene glycol monomethyl ether acetate were introduced into a reaction vessel equipped with a thermometer, stirrer, gas inlet tube, cooling tube, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90°C. On the other hand, as the dropping tank (A), 10.0 parts of N-benzylmaleimide, 29.0 parts of 2-ethylhexyl acrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 31.0 parts of glycidyl methacrylate, and propylene glycol were added to a beaker. A mixture of 30 parts of monomethyl ether acetate and 2.0 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl (registered trademark) O" manufactured by Nippon Oil Co., Ltd.) was prepared, and in the dropping tank (B), A stirring mixture of 2.0 parts of n-dodecylmercaptan and 31.33 parts of propylene glycol monomethyl ether acetate was prepared. After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes. 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, followed by dilution with 40 parts of propylene glycol monomethyl ether. Thus, copolymer solution A-15 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 16)

Preparation of copolymer solution A-16 (solution of SAH adduct of BzMI-CHMA-HEMA-GMA copolymer)

83.6 parts of propylene glycol monomethyl ether acetate were introduced into a reaction tank equipped with a thermometer, stirrer, gas inlet pipe, cooling pipe, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90 degreeC. On the other hand, as the dropping tank (A), in a beaker, 20.0 parts of N-benzylmaleimide, 25.0 parts of cyclohexyl methacrylate, 50.0 parts of 2-hydroxyethyl methacrylate, 5.0 parts of glycidyl methacrylate, and propylene glycol mono A mixture of 50 parts of methyl ether acetate and 2.0 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl (registered trademark) O” manufactured by Nihon Oil Co., Ltd.) was prepared, and in the dropping tank (B), n - Prepared by stirring and mixing 0.3 parts of dodecylmercaptan and 99.70 parts of propylene glycol monomethyl ether acetate. After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes. Then, after cooling to room temperature, it was made to react with 34.6 parts of succinic anhydride, 0.40 part of triethylamine as a catalyst, and 78.9 parts of propylene glycol monomethyl ether acetate at 60 degreeC for 10 hours, and copolymer solution A-16 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 17)

Preparation of copolymer solution A-17 (solution of SAH adduct of AA adduct of BzMI-CHMA-HEMA-GMA copolymer)

16.6 parts of propylene glycol monomethyl ether acetate were introduced into a reaction tank equipped with a thermometer, stirrer, gas inlet pipe, cooling pipe, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90 degreeC. On the other hand, as a dropping tank (A), in a beaker, 30.0 parts of N-benzylmaleimide, 10.0 parts of cyclohexyl methacrylate, 10.0 parts of 2-hydroxyethyl methacrylate, 50.0 parts of glycidyl methacrylate, and propylene glycol mono A mixture of 30.0 parts of methyl ether acetate and 2.0 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl (registered trademark) O" manufactured by Nihon Oil Co., Ltd.) was prepared, and in the dropping tank (B), n - Prepared by stirring and mixing 6.0 parts of dodecyl mercaptan and 82.24 parts of propylene glycol monomethyl ether acetate. After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes. Then, after cooling to room temperature, 22.8 parts of acrylic acid, 0.37 part of triphenylphosphine as a catalyst, and 0.18 part 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 anhydride react at 60 degreeC for 8 hours, it diluted with 118 parts of propylene glycol monomethyl ether, and copolymer solution A-17 was obtained. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 18)

Preparation of copolymer solution A-18 (solution of SAH adduct of Karenz MOI adduct of BzMI-CHMA-HEMA-GMA copolymer)

78.6 parts of propylene glycol monomethyl ether acetate were introduced into a reaction tank equipped with a thermometer, stirrer, gas inlet pipe, cooling pipe, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90 degreeC. On the other hand, as the dropping tank (A), in a beaker, 10.0 parts of N-benzylmaleimide, 29.3 parts of cyclohexyl methacrylate, 40.0 parts of 2-hydroxyethyl methacrylate, 20.7 parts of glycidyl methacrylate, and propylene glycol mono A mixture of 10.0 parts of methyl ether acetate and 6.0 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl (registered trademark) O” manufactured by Nihon Oil Co., Ltd.) was prepared, and in the dropping tank (B), n - Prepared by stirring and mixing 2.0 parts of dodecylmercaptan and 48.00 parts of propylene glycol monomethyl ether acetate. After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, 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 part of Antage W-400 were reacted at 90°C for 8 hours. . Then, after cooling to room temperature, 14.6 parts of succinic anhydride and 0.36 parts of triethylamine as a catalyst were reacted at 60°C for 10 hours to obtain copolymer solution A-18. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 19)

Preparation of copolymer solution B-1 (BzMI-CHMA-HEMA-cyclomer M100-MAA copolymer)

145.3 parts of propylene glycol monomethyl ether acetate were introduced into a reaction tank equipped with a thermometer, stirrer, gas inlet pipe, cooling pipe, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90 degreeC. On the other hand, as the dropping tank (A), 10.0 parts of N-benzylmaleimide, 47.4 parts of cyclohexyl methacrylate, 13.45 parts of 2-hydroxyethyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate ( 20.25 parts of "Cyclomer M100 (registered trademark)" manufactured by Daicel Co., Ltd., 8.9 parts of methacrylic acid, 10.0 parts of propylene glycol monomethyl ether acetate, t-butyl peroxypivalate (manufactured by Arkema Yoshitomi, "Luperox 11 ( Registered trademark)” was prepared by stirring and mixing 2.7 parts of the mixture, and prepared by stirring and mixing 2.0 parts of n-dodecylmercaptan and 78 parts of propylene glycol monomethyl ether acetate in the dropping tank (B). After the temperature of the reaction tank reached 70°C, while maintaining the same temperature, dripping was started from the dropping tank over 3 hours to perform polymerization. After completion of dropping, the temperature was maintained at 70°C for 30 minutes, then the temperature was raised to 80°C, and aging was performed for 180 minutes to obtain copolymer solution B-1. Various physical properties of the obtained copolymer are shown in Table 1.

(Production Example 20)

Preparation of copolymer solution B-2 (BzMI-CHMA-HEMA-GMA-MAA copolymer)

145.3 parts of propylene glycol monomethyl ether acetate was introduced into a reaction tank equipped with a thermometer, stirrer, gas inlet pipe, cooling pipe, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 70 degreeC. On the other hand, as the dropping tank (A), 10.0 parts of N-benzylmaleimide, 52.95 parts of cyclohexyl methacrylate, 13.45 parts of 2-hydroxyethyl methacrylate, 14.7 parts of glycidyl methacrylate, and methacrylic acid were added to a beaker. A mixture of 8.9 parts of acid, 10.0 parts of propylene glycol monomethyl ether acetate, and 2.7 parts of t-butylperoxypivalate (“Luperox 11 (registered trademark)” manufactured by Arkema Yoshitomi) was stirred and mixed to prepare a dropping tank (B) Then, what stirred and mixed 2.0 parts of n-dodecyl mercaptan and 78 parts of propylene glycol monomethyl ether acetate was prepared. After the temperature of the reaction tank reached 70°C, while maintaining the same temperature, dripping was started from the dropping tank over 3 hours to perform polymerization. After completion of the dropping, the temperature was maintained at 70°C for 30 minutes, then the temperature was raised to 80°C, and aging was performed for 180 minutes to obtain copolymer solution B-2. Various physical properties of the obtained copolymer are shown in Table 1.

In addition, description in Table 1 is as follows.

BzMI: N-benzylmaleimide

AMA: α-(allyloxymethyl)methyl acrylate

MD: dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate

CHMI: N-cyclohexylmaleimide

CHMA: cyclohexyl methacrylate

VT: Vinyltoluene

2EHA: 2-ethylhexyl acrylate

DCPMA: dicyclopentanyl methacrylate

TBMA: tert-butyl methacrylate

HEMA: Methacrylic acid-2-hydroxyethyl

HEAA: N-hydroxyethyl acrylamide

GLMA: Glycerin Monomethacrylate

M100: 3,4-epoxycyclohexylmethyl methacrylate

GMA: Glycidyl methacrylate

NIPAM: N-isopropylacrylamide

MAA: methacrylic acid

AA: acrylic acid

Karenz MOI: 2-methacryloyloxyethyl isocyanate

SAH: Succinic Anhydride

(Preparation of Pigment Dispersion 1)

12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Dispalon DA-7301 as a dispersant, and C.I. 2.25 parts of Pigment Green 58, and C.I. 1.5 parts of Pigment Yellow 138 were mixed and the pigment dispersion 1 (22 mass % of solid content) was obtained by making it disperse|distribute in a paint shaker for 3 hours.

(Example 1)

As solid content, Irgacure OXE-02 (manufactured by BASF Japan Co., Ltd.) is 5.0 parts as 30.0 parts of dipentaerythritol hexaacrylate as 35.0 parts of copolymer solution A-1 and radically polymerizable compound, and radical polymerizable photopolymerization initiator for copolymer solution A-1. , The photosensitive resin composition 1 was obtained by adding and stirring 30.0 parts of the pigment dispersion 1 and further diluting solvent (propylene glycol monomethyl ether acetate) so that it might become 20% of solid content concentration.

(Examples 2 to 18, Comparative Examples 1 to 2)

Photosensitive resin compositions 2 to 20 were obtained in the same manner as in Example 1 except that they were formulated as shown in Table 2.

The solvent resistance of the obtained photosensitive resin compositions 1-20 was evaluated. A result is shown in Table 2.

From 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 having an epoxy equivalent of 20000 or less has good curability even under low-temperature curing conditions of 90 ° C. or 110 ° C., It turned out that the hardened|cured material excellent in solvent resistance was provided.

Example 19, Comparative Example 3

(Confirmation of preservation stability)

The following operation was performed in order to investigate the effect of the storage stability by the diluting solvent. 2 at 40°C using a copolymer solution in which 20 parts of a diluting solvent (equivalent to 66.7% by mass relative to 100% by mass of the copolymer solid content) was added to 100 parts (as is) of the copolymer solution A-2. Changes in physical properties (weight average molecular weight and viscosity) of the copolymer before and after storage for a week were confirmed. As the diluting 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 resulting copolymer solution.

Regarding the weight average molecular weight as the amount of change, the ratio (%) of the difference between the weight average molecular weight before and after storage relative to the weight average molecular weight before storage was shown. Regarding the viscosity, the ratio (%) of the difference between the viscosity before and after storage with respect to the viscosity before storage was shown.

From Table 3, when propylene glycol monomethyl ether, which is an alcohol-based solvent, was added, the amount of change in weight average molecular weight after storage and the amount of change in viscosity were small compared to the case where propylene glycol monomethyl ether acetate was added, resulting in a copolymer It was found that the storage stability of was excellent.

(Production Example 21)

Preparation of Copolymer Solution A-19

105.3 parts of propylene glycol monomethyl ether acetate was introduced into a reaction tank equipped with a thermometer, stirrer, gas inlet pipe, cooling pipe, and dropping tank inlet, and after nitrogen substitution, it was heated and the temperature was raised to 90 degreeC. On the other hand, as the dropping tank (A), in a beaker, 10.0 parts of N-benzylmaleimide, 27.5 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 32.5 parts of glycidyl methacrylate, and propylene glycol mono A mixture of 30 parts of methyl ether acetate and 2.0 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl (registered trademark) O" manufactured by Japan Oil Co., Ltd.) was prepared, and in the dropping tank (B), n - Prepared by stirring and mixing 2.0 parts of dodecylmercaptan and 98.0 parts of propylene glycol monomethyl ether acetate. After the temperature of the reaction tank reached 90°C, dripping was started over 3 hours from the dropping tank while maintaining the temperature, and polymerization was performed. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes. Then, after cooling to room temperature, 11.5 parts of succinic anhydride, 0.33 part of triethylamine as a catalyst, and 29.0 parts of propylene glycol monomethyl ether acetate were added, and it was made to react at 60 degreeC for 7 hours. Then, 42.0 parts of propylene glycol monomethyl ether was added so that solid content might be 27%, and copolymer solution A-19 was obtained. Various physical properties of the obtained copolymer are shown in Table 4.

(Production Example 22)

Preparation of copolymer solution A-20

Copolymer solution A-20 was obtained in the same preparation method as in 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 copolymer are shown in Table 4.

In addition, description in Table 4 is as follows.

BzMI: N-benzylmaleimide

CHMA: cyclohexyl methacrylate

HEMA: Methacrylic acid-2-hydroxyethyl

GMA: Glycidyl methacrylate

SAH: Succinic Anhydride

TEA: triethylamine

(Example 20)

As a solid content, 35.0 parts of copolymer solution A-19, 30.0 parts of dipentaerythritol hexaacrylate as a radically polymerizable compound, and 5.0 parts of Irgacure OXE-02 (manufactured by BASF Japan) as a radically polymerizable photopolymerization initiator , 30.0 parts of Pigment Dispersion 1, 1.0 parts of P-2M (light ester P-2M, pKa: 1.29, manufactured by Kyoeisha Chemical), and further dilution solvent (propylene glycol monomethyl ether acetate), solid content concentration 20 The photosensitive resin composition 21 was obtained by adding and stirring so that it might become %.

(Examples 21 to 23)

Photosensitive resin compositions 22 to 24 were obtained in the same manner as in Example 20 except that they were formulated as shown in Table 5.

The solvent resistance of the obtained photosensitive resin compositions 21-24 was evaluated. A result is shown in Table 5.

From Table 5, it can be seen that the photosensitive resin composition containing a copolymer having an epoxy group-containing structural unit and an acid group-containing structural unit and having an epoxy equivalent of 20000 or less has good curability and excellent solvent resistance even under curing conditions at a low temperature of 90°C. can

Examples 24 to 40

(Confirmation of preservation stability)

With respect to 100 parts of the copolymer solution (as is), in the amount shown in Table 6 or Table 7, a diluting solvent (propylene glycol monomethyl ether) and P-1M, P-2M, MSA, or ACA were added and airborne A coalescence solution was prepared. The amount of the dilution solvent corresponds to 129.6 mass% with respect to 100 mass% of copolymer solid content in Table 6 (35 parts), and corresponds to 29.6 mass% with respect to 100 mass% of copolymer solid content in Table 7 (8 parts). Using the obtained copolymer solution, the change in physical properties (viscosity) of the copolymer solution before and after storage at 40°C for 1 to 2 weeks was confirmed. Table 6 and Table 7 show changes in physical properties of the resulting copolymer solution. As the amount of change in viscosity (thickening ratio), the ratio (%) of the difference in viscosity before and after storage with respect to the viscosity before storage was shown. Moreover, content of the acid compound (P-1M, P-2M, MSA, ACA) with respect to 100 mol% of the basic compound (TEA) in the copolymer solution was shown in the table|surface.

In addition, description in Table 6 and Table 7 is as follows.

P-1M: light ester P-1M (manufactured by Kyoeisha Chemical) 2-metacroyloxyethyl acid phosphate, pKa: 1.78, molecular weight: 210.12

P-2M: light ester P-2M (manufactured by Kyoeisha Chemical) 2-methacroyloxyethyl acid 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 Tables 6 and 7, in the copolymer solution containing a copolymer having an epoxy group-containing structural unit and an acid group-containing structural unit and having an epoxy equivalent of 20000 or less, and a protic polar solvent, an acid compound having a pKa of 4.2 or less. It was confirmed that the thickening rate after storage was lowered by including the, and the storage stability was excellent.

Claims (14)

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

(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 an epoxy group-containing 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 bonded chain having a length of 2 atoms or more. Y represents an acid group represents 0 or 1.) According to claim 1,
A copolymer characterized in that the structural unit (A) includes 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.) According to claim 1 or 2,
A copolymer characterized in that the structural unit (B) includes 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. ) According to any one of claims 1 to 3,
Further, a copolymer characterized in that it is a copolymer having a ring structure in the main chain. A copolymer solution characterized by comprising the copolymer according to any one of claims 1 to 4 and a protic polar solvent. According to claim 5,
A copolymer solution characterized by further comprising an acid compound having a pKa of 4.2 or less. According to claim 5 or 6,
Additionally, a copolymer solution characterized by comprising a phosphoric acid derivative. According to any one of claims 5 to 7,
Additionally, a copolymer solution characterized by containing a basic compound. A copolymer according to any one of claims 1 to 4 or a copolymer solution according to any one of claims 5 to 8, a polymerizable compound, and a photopolymerization initiator, characterized in that A photosensitive resin composition. According to claim 9,
Additionally, a photosensitive resin composition comprising a colorant. According to claim 9 or 10,
A photosensitive resin composition characterized in that it is for negative type. The copolymer according to any one of claims 1 to 4, the copolymer solution according to any one of claims 5 to 8, or the photosensitive resin according to any one of claims 9 to 11 Cured product of the composition. A step of polymerizing a monomer component containing an epoxy group-containing monomer represented by the following formula (a) and a hydroxyl group-containing monomer represented by the following formula (b1);
A method for producing a copolymer characterized by including 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 an epoxy group-containing 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 bonded chain having a length of 2 atoms or more. Y represents an acid group.)

(In formula (b3), R ⁵ represents a bonded chain having a length of 2 atoms or more.) A step of polymerizing a monomer component containing 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 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;
A method for producing a copolymer solution characterized by comprising a step of adding an acid compound having a pKa of 4.2 or less and a protic polar solvent.

(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 an epoxy group-containing 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 bonded chain having a length of 2 atoms or more. Y represents an acid group.)

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