WO2021182232A1

WO2021182232A1 - Photosensitive resin composition, cured product, color filter, display device member and display device

Info

Publication number: WO2021182232A1
Application number: PCT/JP2021/008168
Authority: WO
Inventors: 中川　泰伸
Original assignee: 株式会社ダイセル
Priority date: 2020-03-09
Filing date: 2021-03-03
Publication date: 2021-09-16
Also published as: TW202138404A; CN115380248A; KR20220152541A

Abstract

Provided is a photosensitive resin composition which exhibits excellent storage stability and curing reaction properties and which gives a cured product having excellent solvent resistance. This photosensitive resin composition contains an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent. The alkali-soluble resin is a copolymer that contains a constituent unit (A) derived from an unsaturated carboxylic acid or an anhydride thereof and a constituent unit (B) derived from a compound represented by formula (1) (in the formula, R¹ and R² each denote a hydrogen atom or an alkyl group having 1-7 carbon atoms. X denotes a single bond, a divalent hydrocarbon group, or the like. Y denotes a methylene group or ethylene group that may have an alkyl group having 1-3 carbon atoms as a substituent group, or the like. n is an integer from 0 to 7). The copolymer has an exothermic peak top temperature of 180-220°C, which appears when the temperature is increased at a rate of 5°C/minute using a differential scanning calorimeter.

Description

Photosensitive resin composition, cured product, color filter, display device member, and display device

The present disclosure relates to a photosensitive resin composition, a cured product, a color filter, a display device member, and a display device. The present application claims the priority of Japanese Patent Application No. 2020-039964 and Japanese Patent Application No. 2020-039965 filed in Japan on March 9, 2020, the contents of which are incorporated herein by reference.

As the photosensitive resin composition used in producing an insulating film, a color filter, a color filter protective film, and a microlens, a resin composition containing an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator, and further. Resin compositions containing colorants (pigments and dyes) are known.

Patent Documents 1 and 4 disclose copolymers containing methacrylic acid and glycidyl methacrylate as constituent monomers as the alkali-soluble resin. Patent Documents 2 and 5 disclose copolymers containing methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate as constituent monomers as the alkali-soluble resin. There is. Patent Document 3 discloses a copolymer containing methacrylic acid and benzyl methacrylate as constituent monomers as the alkali-soluble resin.

Japanese Unexamined Patent Publication No. 11-133600 Japanese Unexamined Patent Publication No. 2006-171160 Japanese Unexamined Patent Publication No. 9-134004 Japanese Unexamined Patent Publication No. 2011-237728 Japanese Unexamined Patent Publication No. 2007-333847

However, the photosensitive resin compositions disclosed in Patent Documents 1 and 4 have a drawback of low stability such as thickening with time. In addition, the solvent resistance of the cured product was not sufficient. Although the photosensitive resin compositions disclosed in Patent Documents 2 and 5 are excellent in storage stability, they have poor reactivity with carboxylic acids and require a curing temperature of 230 ° C. or higher. The photosensitive resin composition disclosed in Patent Document 3 has a drawback that the solvent resistance of the cured product is low.

Therefore, an object of the present invention is to provide a photosensitive resin composition having excellent storage stability, excellent curing reactivity, and excellent solvent resistance of the cured product.
Another object of the present invention is to provide a cured product of a photosensitive resin composition having the above characteristics, a color filter which is the cured product, and a display device member or display device provided with the color filter. To provide.

As a result of diligent studies to achieve the above object, the present inventor has made a photosensitive resin composition using a copolymer containing a specific structural unit as an alkali-soluble resin and having an exothermic peak top temperature of 180 to 220 ° C. According to the report, it was found that the product has excellent storage stability, cures even at a relatively low temperature, and has excellent solvent resistance of the cured product. The invention according to the present disclosure has been completed based on these findings.

That is, the present disclosure includes an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.
The alkali-soluble resin contains a structural unit (A) derived from an unsaturated carboxylic acid or an anhydride thereof, and the following formula (1).

(In the formula, R ¹ and R ² are the same or different, respectively, and represent a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. X is a divalent hydrocarbon group which may contain a single bond or a hetero atom. Y represents a methylene group or an ethylene group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom which may be bonded to an oxygen atom. N is 0. Indicates an integer of ~ 7.)
It is a copolymer containing the structural unit (B) derived from the compound represented by, and the exothermic peak top temperature that appears when the temperature is raised at a rate of 5 ° C./min using a differential scanning calorimeter is 180. Provided is a photosensitive resin composition which is a copolymer at ~ 220 ° C.

The copolymer may further contain a structural unit (C) derived from at least one compound selected from the group consisting of the following (c1) to (c4).
(C1) Styrene (c2) N-substituted maleimide (c3) N-vinyl compound (c4) which may be substituted with an alkyl group The following formula (2)

(In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R ¹² represents a hydrocarbon group which may contain a hetero atom. Z represents a hetero atom.)
Unsaturated carboxylic acid derivative represented by

The ratio of the structural unit (A) to all the structural units of the copolymer is 2 to 60% by weight, the ratio of the structural unit (B) is 40 to 98% by weight, and the ratio of the structural unit (C) is 0 to 0 to. It may be 85% by weight.

The photosensitive resin composition of the present disclosure may further contain a coloring material.

The coloring material may be a pigment and / or a dye.

The present disclosure also provides a cured product of the photosensitive resin composition described above.

The present disclosure also provides a color filter which is a cured product of the above-mentioned photosensitive resin composition.

The present disclosure further provides a display device member or display device including the above-mentioned color filter.

According to the invention according to the present disclosure, there is provided a photosensitive resin composition having excellent storage stability, excellent curing reactivity, and excellent solvent resistance of the cured product. Further, a cured product of a photosensitive resin composition having the above characteristics, a color filter which is the cured product, and a display device member or display device provided with the color filter are provided.

The photosensitive resin composition according to the present disclosure is mainly used as a forming material for an insulating film, a color filter protective film, a microlens, a coloring pattern, etc., and a transparent film, and is an alkali-soluble resin and a photopolymerizable compound. , Photopolymerization initiator, and solvent. Further, the photosensitive resin composition according to the present disclosure may be a photosensitive resin composition further containing a coloring material.

<Alkali-soluble resin>
In the present disclosure, the alkali-soluble resin includes a structural unit (A) derived from an unsaturated carboxylic acid or an anhydride thereof and a structural unit (B) derived from a compound represented by the formula (1). A copolymer having an exothermic peak top temperature of 180 to 220 ° C. that appears when the temperature is raised at a rate of 5 ° C./min using a differential scanning calorimeter is used. The copolymer may further contain a structural unit (C) derived from at least one compound selected from the group consisting of (c1) to (c4). Further, the structural unit (D) described later may be included as a structural unit other than the structural units (A) to (C).

[Structural unit (A)]
The structural unit (A) can be introduced into the copolymer by subjecting an unsaturated carboxylic acid or an acid anhydride thereof (a) to the copolymer.

The unsaturated carboxylic acid or its acid anhydride (a) is not particularly limited, but for example, α, β-unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; itaconic acid, maleic acid, fumaric acid and the like. Α, β-unsaturated dicarboxylic acid; α, β-unsaturated monocarboxylic acid anhydride such as methacrylic acid anhydride; α, β-unsaturated dicarboxylic acid anhydride such as maleic anhydride and itaconic anhydride. Be done. Among these, acrylic acid and methacrylic acid are particularly preferable from the viewpoint of copolymerizability and developability. The unsaturated carboxylic acid or its acid anhydride (a) can be used alone or in combination of two or more.

The ratio (content) of the constituent unit (A) to all the constituent units of the copolymer is not particularly limited, but is preferably 2 to 60% by weight, more preferably 3 to 40% by weight, still more preferably 5 to 5 to 60% by weight, for example. 20% by weight. When the ratio of the structural unit (A) is within the above range, the cured product tends to be excellent in solvent resistance and developability. In the present disclosure, the ratio of the constituent unit to the copolymer is based on the weight of the compound (monomer) used for the copolymerization. For example, the ratio of the constituent unit (A) to the copolymer is the ratio of the amount of the unsaturated carboxylic acid or the acid anhydride (a) used to the total amount (100% by weight) of the compounds used for the copolymerization. means.

[Structural unit (B)]
The structural unit (B) can be introduced into the copolymer by subjecting the compound represented by the following formula (1) to the copolymer.

In formula (1), R ¹ and R ² represent hydrogen atoms or alkyl groups having 1 to 7 carbon atoms, which are the same or different from each other. X represents a divalent hydrocarbon group that may contain a single bond or a heteroatom. Y represents a methylene group or an ethylene group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom which may be bonded to the oxygen atom. n represents an integer from 0 to 7.

Examples of the alkyl group having 1 to 7 carbon atoms in R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a pentyl group, a hexyl group, and a heptyl group. And so on. When n is 2 or more, n R ^2s may be the same or different. R ¹ and R ² are preferably a hydrogen atom, a methyl group, or an ethyl group from the viewpoint of copolymerizability and reactivity.

In a divalent hydrocarbon group which may contain a heteroatom of X, the heteroatom may be bonded to the terminal of the hydrocarbon group or may be interposed between carbon atoms constituting the hydrocarbon group. .. Heteroatoms are not particularly limited, and examples thereof include nitrogen atoms, oxygen atoms, and sulfur atoms.

As the divalent hydrocarbon group which may contain the hetero atom, for example, an alkylene group such as a methylene group, an ethylene group, a propylene group and a trimethylene group (preferably an alkylene group having 1 to 12 carbon atoms is preferable and the carbon number is 1). An alkylene group of to 6 is more preferable, and an alkylene group having 1 to 3 carbon atoms is particularly preferable); a thioalkylene group such as a thiomethylene group, a thioethylene group, or a thiopropylene group (a thioalkylene group having 1 to 12 carbon atoms is preferable, and carbon is preferable. A thioalkylene group having a number of 1 to 6 is more preferable); an aminoalkylene group such as an aminomethylene group, an aminoethylene group and an aminopropylene group (preferably an aminoalkylene group having 1 to 12 carbon atoms and an aminoalkylene group having 1 to 6 carbon atoms). Groups are more preferred) and the like. Among these, from the viewpoint of storage stability, an alkylene group having 1 to 3 carbon atoms is preferable, and a methylene group is more preferable.

The methylene group or ethylene group which may have an alkyl group having 1 to 3 carbon atoms as the substituent of Y is not particularly limited, but a methylene group or an ethylene group is preferable, and a methylene group is more preferable.

Examples of the sulfur atom that may be bonded to the oxygen atom of Y include a sulfur atom and a sulfonyl group.

Examples of the compound represented by the formula (1) include a compound represented by the following formula (1a).

^{R 1} , R ² , X, Y, and n in the formula (1a) are the same as those described in the formula (1).

Specific examples of the compound represented by the formula (1) include the following compounds.

The ratio (content) of the constituent unit (B) to all the constituent units of the copolymer is not particularly limited, but is preferably 40 to 98% by weight, more preferably 60 to 95% by weight, still more preferably 75. ~ 90% by weight. When the ratio of the structural unit (B) is within the above range, the cured product tends to be excellent in solvent resistance and developability.

[Structural unit (C)]
The structural unit (C) is styrene (c1) which may be substituted with an alkyl group, N-substituted maleimide (c2), an N-vinyl compound (c3), and an unsaturated carboxylic acid represented by the above formula (2). It is a structural unit derived from at least one compound selected from the group consisting of an acid derivative (c4). The structural unit (C) has a function of imparting hardness to a cured product (cured film), a function of facilitating a copolymerization reaction, a function of increasing solubility in a solvent, a function of enhancing adhesion to a substrate, and the like. ..

The structural unit (C) can be introduced into the copolymer by subjecting at least one compound selected from the group consisting of the above (c1) to (c4) to the copolymer.

(Styrene (c1))
The alkyl group in styrene (c1) which may be substituted with an alkyl group is not particularly limited, but for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a hexyl group and the like. Alkyl groups having 1 to 7 carbon atoms can be mentioned. Among these, an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group is preferable, and a methyl group is more preferable. The alkyl group may be bonded to either a vinyl group of styrene or a benzene ring.

Typical examples of styrene (c1) which may be substituted with an alkyl group include styrene, α-methylstyrene, vinyltoluene (o-vinyltoluene, m-vinyltoluene, p-vinyltoluene) and the like. Styrene (c1), which may be substituted with an alkyl group, can be used alone or in combination of two or more.

(N-substituted maleimide (c2))
Examples of the N-substituted maleimide (c2) include a compound represented by the following formula (3).

In formula (3), R ²¹ represents an organic group.

Examples of the organic group include a hydrocarbon group and a heterocyclic group. Examples of the hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a hexyl group (for example, a C _1-6 alkyl group); a cyclopentyl group, a cyclohexyl group and a cyclooctyl group. Examples thereof include a cycloalkyl group such as an adamantyl group and a norbornyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; and a group in which two or more of these are bonded. Examples of the heterocyclic group include a 5- to 10-membered heterocycloalkyl group and a heteroaryl group containing at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom. ..

The N-substituted maleimide (c2) is not particularly limited, and is, for example, N-alkylmaleimide such as N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide; N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cyclo. Examples thereof include N-cycloalkylmaleimide such as octylmaleimide, N-adamantylmaleimide and N-norbornylmaleimide; N-arylmaleimide such as N-phenylmaleimide; and N-aralkylmaleimide such as N-benzylmaleimide. The N-substituted maleimide (c2) can be used alone or in combination of two or more.

(N-vinyl compound (c3))
The N-vinyl compound (c3) is not particularly limited, but for example, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, N-vinylpyrrolidone, N-vinylcarbazole. , N-vinylpiperidone, N-vinylcaprolactam and the like. The N-vinyl compound (c3) can be used alone or in combination of two or more.

(Unsaturated carboxylic acid derivative (c4))
The unsaturated carboxylic acid derivative (c4) can be represented by the following formula (2).

In formula (2), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R ¹² represents a hydrocarbon group that may contain a heteroatom. Z represents a heteroatom.

Examples of the alkyl group having 1 to 7 carbon atoms in R ¹¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a hexyl group and the like. As R ¹¹ , a hydrogen atom or a methyl group is particularly preferable.

Examples of the hydrocarbon group which may contain a hetero atom in R ¹² include an alkyl group, a heteroalkyl group, an alkenyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, and a group in which two or more of these are linked. Can be mentioned. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.

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

As the heteroalkyl group, for example,-(R ^13- O) m-R ¹⁴ groups (in the formula, R ¹³ represents an alkylene group ^{having 1 to 12 carbon atoms. R 14} is a hydrogen atom or 1 to 12 carbon atoms. (M indicates an integer of 1 or more), -R ^15- NR ¹⁶ R ¹⁷ groups (in the formula, R ¹⁵ indicates an alkylene group having 1 to 12 carbon atoms. R ¹⁶ and R ¹⁷ are. , The same or different, respectively, indicating a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

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

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

Examples of the heterocycloalkyl group include groups containing a cyclic ether structure such as an oxetane ring, an oxoran ring, an oxane ring, and an oxepane ring (for example, a cyclic ether-containing group having a 3-membered ring or more).

Examples of the aryl group include an aryl group having 6 to 12 carbon atoms such as a phenyl group and a naphthyl group.

The unsaturated carboxylic acid derivative (c4) represented by the formula (2) is not particularly limited, and is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and butyl. (Meta) acrylate having an alkyl group such as (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylamino (Meta) acrylate having an alkylamino group such as ethyl (meth) acrylate, N, N-diisopropylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy Hydroxyl-containing (meth) acrylates such as butyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol. (Meta) acrylate having a heteroalkyl group such as polyalkylene glycol (meth) acrylate such as (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate; alkenyl such as allyl (meth) acrylate having a group (meth) acrylate; cyclohexyl (meth) acrylate, 1-adamantyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5,2,1,0 ^2,6] decan-8-ol (meth) acrylate (Meta) acrylate having a monocyclic or polycyclic cycloalkyl group such as; glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 2-ethylglycidyl (meth) acrylate, 2-glycidyloxyethyl (meth) (Meta) acrylate having an epoxy group (oxylanyl group) such as acrylate, 3-glycidyloxypropyl (meth) acrylate, glycidyloxyphenyl (meth) acrylate, oxetanyl (meth) acrylate, 3-methyl-3-oxetanyl (meth) Acrylate, 3-ethyl-3-oxetanyl (meth) acrylate, (3-methyl-3-oxetanyl) meth Lu (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, 2- (3-methyl-3-oxetanyl) ethyl (meth) acrylate, 2- (3-ethyl-3-oxetanyl) ethyl (Meta) acrylate, 2-[(3-Methyl-3-oxetanyl) methyloxy] ethyl (meth) acrylate, 2-[(3-ethyl-3-oxetanyl) methyloxy] ethyl (meth) acrylate, 3-[ (3-Methyl-3-oxetanyl) methyloxy] propyl (meth) acrylate, 3-[(3-ethyl-3-oxetanyl) methyloxy] propyl (meth) acrylate and other (meth) acrylates having an oxetanyl group, tetrahydro (Meta) acrylate having an oxolanyl group such as furfuryl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2- (3,4-epoxycyclohexyl) Contains alicyclic epoxy groups such as ethyl (meth) acrylate, 2- (3,4-epoxycyclohexylmethyloxy) ethyl (meth) acrylate, 3- (3,4-epoxycyclohexylmethyloxy) propyl (meth) acrylate. (Meta) acrylate having a heterocycloalkyl group such as (meth) acrylate (for example, a cyclic ether-containing group having three or more membered rings); (meth) having an aryl group such as phenyl (meth) acrylate and benzyl (meth) acrylate. Aacrylate; 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxipropyltriethoxysilane , 8- (Meta) Acryloxyoctyl Dimethoxysilane and other alkoxysilyl group-containing (meth) acrylates. The unsaturated carboxylic acid derivative (c4) represented by the formula (2) can be used alone or in combination of two or more.

The ratio (content) of the constituent unit (C) to all the constituent units of the copolymer is not particularly limited, but is preferably 0 to 85% by weight, more preferably 1 to 60% by weight, still more preferably 2. ~ 40% by weight. When the ratio of the structural unit (C) is within the above range, the solvent resistance of the cured product tends to be excellent.

[Structural unit (D)]
The copolymer in the present disclosure may contain a structural unit (D) other than the structural units (A) to (C). Examples of the structural unit (D) include a structural unit derived from (meth) acrylamide and (meth) acrylonitrile.

When the copolymer in the present disclosure contains the constituent unit (A) and the constituent unit (B) and does not include the constituent unit (C), the total amount of the constituent unit (A) and the constituent unit (B) is the total amount. It is preferably 90% by weight or more, more preferably 95% by weight or more, still more preferably 99% by weight or more, and may be substantially 100% by weight with respect to the constituent unit. When the copolymer in the present disclosure contains a structural unit (A), a structural unit (B), and a structural unit (C), the total amount of the structural units (A) to (C) is relative to all the structural units. It is preferably 90% by weight or more, more preferably 95% by weight or more, still more preferably 99% by weight or more, and may be substantially 100% by weight.

The weight average molecular weight (Mw) of the copolymer is not particularly limited, but is preferably 1000 to 10000, more preferably 3000 to 300,000, and further preferably 5000 to 100,000. The molecular weight distribution of the copolymer (ratio of weight average molecular weight to number average molecular weight: Mw / Mn) is not particularly limited, but is preferably 5.0 or less, more preferably 1.0 to 4.5, for example. , More preferably 1.0 to 4.0. In the present disclosure, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured by, for example, using polystyrene as a standard substance by GPC, but were measured by the method used in the examples. It is preferable that it is one.

The polymer in the present disclosure has a heat generation peak top temperature of 180 to 220 ° C. that appears when the temperature is raised at a rate of 5 ° C./min using a differential scanning calorimeter. In the present disclosure, the exothermic peak top temperature is preferably measured by, for example, the method used in the examples described later.

The copolymer in the present disclosure functions as a binder resin for the photosensitive resin composition according to the present disclosure.

<Method for producing copolymer>
The copolymer in the present disclosure includes an unsaturated carboxylic acid or an anhydride thereof (a), and a compound (b) having a polycyclic aliphatic group having an epoxy group on the ring and a group having an unsaturated bond. If necessary, it can be produced by subjecting at least one compound selected from the group consisting of (c1) to (c4) to the copolymer and the compound corresponding to the structural unit (D). .. Hereinafter, compounds that can be introduced into a copolymer such as unsaturated carboxylic acid or its anhydride (a) may be collectively referred to as "monomer".

In the method for producing a copolymer of the present disclosure, the copolymer may be subjected to copolymerization in the presence of a polymerization initiator. As the polymerization initiator, a conventional or known radical polymerization initiator can be used, and for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2 , 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis (2-methylpropionate), diethyl-2,2'-azobis (2-methylpropio) Nate), azo compounds such as dibutyl-2,2'-azobis (2-methylpropionate), benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, 1,1-bis (t-butyl peroxy) cyclohexane and the like. Organic peroxides, hydrogen peroxide and the like can be mentioned. When a peroxide is used as a radical polymerization initiator, a reducing agent may be combined to form a redox-type initiator. Of these, azo compounds are preferable, and 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), and dimethyl-2,2'-azobis (2-methylpropionate) are preferable. ) Is more preferable.

The amount of the polymerization initiator used can be appropriately selected as long as it does not impair smooth copolymerization, and is not particularly limited. For example, 1 to 20 parts by weight is preferable with respect to the total amount of the monomers (100 parts by weight). It is preferably 3 to 15 parts by weight.

In the present disclosure, the copolymerization can be carried out by a conventional method used for producing an acrylic polymer or a styrene polymer, such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, and emulsion polymerization. The monomer and the polymerization initiator may be collectively supplied to the reaction system, or a part or all of them may be added dropwise to the reaction system. For example, a method of dropping a solution of a polymerization initiator dissolved in a polymerization solvent into a mixture of a monomer or a monomer kept at a constant temperature and a polymerization solvent to carry out the polymerization, or a method of preliminarily starting a monomer and polymerization. A method (drop polymerization method) or the like in which a solution obtained by dissolving an agent in a polymerization solvent is dropped into a polymerization solvent maintained at a constant temperature and polymerized can be adopted.

The copolymer in the present disclosure is preferably copolymerized in a polymerization solvent. The polymerization solvent can be appropriately selected depending on the monomer composition and the like, and for example, ether (diethyl ether; ethylene glycol mono or dialkyl ether, diethylene glycol mono or dialkyl ether, propylene glycol mono or dialkyl ether, propylene glycol mono or diaryl ether, diaryl ether, di. Propropylene glycol mono or dialkyl ether, tripropylene glycol mono or dialkyl ether, 1,3-propanediol mono or dialkyl ether, 1,3-butanediol mono or dialkyl ether, 1,4-butanediol mono or dialkyl ether, glycerin mono , Chain ethers such as glycol ethers such as di or trialkyl ethers; cyclic ethers such as tetrahydrofuran and dioxane), esters (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, etc.) , Caroxyesters such as ethyl 3-ethoxypropionate, C _5-6 cycloalkanediol mono or diacetate, C _5-6 cycloalkanodimethanol mono or diacetate; ethylene glycol monoalkyl ether acetate, ethylene glycol mono or Diacetate, diethylene glycol monoalkyl ether acetate, diethylene glycol mono or diacetate, propylene glycol monoalkyl ether acetate, propylene glycol mono or diacetate, dipropylene glycol monoalkyl ether acetate, dipropylene glycol mono or diacetate, 1,3-propane Diol monoalkyl ether acetate, 1,3-propanediol mono or diacetate, 1,3-butanediol monoalkyl ether acetate, 1,3-butanediol mono or diacetate, 1,4-butanediol monoalkyl ether acetate, 1,4-Butanediol mono or diacetate, glycerin mono, di or triacetate, glycerin mono or di C _1-4 alkyl ether di or monoacetate, tripropylene glycol monoalkyl ether acetate, tripropylene glycol mono or diacetate, etc. Glycol acetates or glycol ether acetates, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexe N-1-one, etc.), Amid (N, N-dimethylacetamide, N, N-dimethylformamide, etc.), Sulfoxide (dimethylsulfoxide, etc.), Alcohol (methanol, ethanol, propanol, C _5-6 cycloalkanediol, C _5-6 cycloalkanedimethanol, etc.), hydrocarbons (aromatic hydrocarbons such as benzene, toluene, xylene, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, etc.), mixed solvents, etc. Can be mentioned.

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

The reaction solution containing the copolymer obtained by the above method can be purified by subjecting it to precipitation or reprecipitation, if necessary. The solvent used for precipitation or reprecipitation may be either an organic solvent or water, or a mixed solvent thereof. Examples of the organic solvent include hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene) and halogenation. Hydrocarbons (halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene), nitro compounds (nitromethane, nitroethane, etc.), nitriles (acetriform, benzonitrile, etc.) Etc.), ether (chain ether such as diethyl ether, diisopropyl ether, dimethoxyethane; cyclic ether such as tetrahydrofuran, dioxane), ketone (acetone, methyl ethyl ketone, diisobutyl ketone, etc.), ester (ethyl acetate, butyl acetate, etc.), carbonate Examples thereof include (dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), alcohols (methanol, ethanol, propanol, isopropyl alcohol, butanol, etc.), carboxylic acids (acetic acid, etc.), and mixed solvents containing these solvents.

<Color material>
In the present disclosure, the coloring material (coloring agent) may be any as long as it has coloring properties, and the color and material can be appropriately selected according to the use of the color filter and the like. Specifically, any of pigments, dyes and natural dyes can be used as the coloring material, but since high color purity, brightness, contrast and the like are required for color filter applications, pigments and / or dyes Is preferable.

The pigment may be either an organic pigment or an inorganic pigment, and examples of the organic pigment include compounds classified as pigments in the Color Index (CI; The Society of Dyers and Colorists). .. Specifically, those having the following color index (CI) names can be mentioned.

C. I. Pigment Yellow 1, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 16, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 20, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 31, C.I. I. Pigment Yellow 55, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 125, C.I. I. Pigment Yellow 137, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 148, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 153, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 166, C.I. I. Pigment Yellow 168, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 194, C.I. I. Pigment Yellow 211, C.I. I. Pigment Yellow 214 and other yellow pigments.

C. I. Pigment Orange 5, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 14, C.I. I. Pigment Orange 24, C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 36, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 40, C.I. I. Pigment Orange 42, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 46, C.I. I. Pigment Orange 49, C.I. I. Pigment Orange 51, C.I. I. Pigment Orange 55, C.I. I. Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 65, C.I. I. Pigment Orange 68, C.I. I. Pigment Orange 70, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 72, C.I. I. Pigment Orange 73, C.I. I. An orange pigment such as Pigment Orange 74.

C. I. Pigment Red 1, C.I. I. Pigment Red 2, C.I. I. Pigment Red 5, C.I. I. Pigment Red 9, C.I. I. Pigment Red 17, C.I. I. Pigment Red 31, C.I. I. Pigment Red 32, C.I. I. Pigment Red 41, C.I. I. Pigment Red 97, C.I. I. Pigment Red 105, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 144, C.I. I. Pigment Red 149, C.I. I. Pigment Red 166, C.I. I. Pigment Red 168, C.I. I. Pigment Red 170, C.I. I. Pigment Red 171 and C.I. I. Pigment Red 175, C.I. I. Pigment Red 176, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 179, C.I. I. Pigment Red 180, C.I. I. Pigment Red 185, C.I. I. Pigment Red 187, C.I. I. Pigment Red 192, C.I. I. Pigment Red 202, C.I. I. Pigment Red 206, C.I. I. Pigment Red 207, C.I. I. Pigment Red 209, C.I. I. Pigment Red 214, C.I. I. Pigment Red 215, C.I. I. Pigment Red 216, C.I. I. Pigment Red 220, C.I. I. Pigment Red 221 and C.I. I. Pigment Red 224, C.I. I. Pigment Red 242, C.I. I. Pigment Red 243, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 262, C.I. I. Pigment Red 264, C.I. I. Pigment Red 265, C.I. I. Red pigments such as Pigment Red 272.

C. I. Pigment Violet 1, C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 36, C.I. I. Violet color pigments such as Pigment Violet 38.

C. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 60, C.I. I. Blue pigments such as Pigment Blue 80.

C. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58 and other green pigments.

C. I. Pigment Brown 23, C.I. I. A brown pigment such as Pigment Brown 25.

C. I. Pigment Black 1, C.I. I. Black pigments such as Pigment Black 7.

Examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, and chromium oxide. Examples thereof include green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

In the present disclosure, the pigment can also be purified and used by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination thereof. Further, the pigment may be used by modifying the surface of the particles with a resin.

Further, the dye can be appropriately selected from various oil-soluble dyes, direct dyes, acid dyes, metal complex dyes and the like, and for example, the following color index (CI) names are given. You can list what has been done.

C. I. Solvent Yellow 4, C.I. I. Solvent Yellow 14, C.I. I. Solvent Yellow 15, C.I. I. Solvent Yellow 24, C.I. I. Solvent Yellow 82, C.I. I. Solvent Yellow 88, C.I. I. Solvent Yellow 94, C.I. I. Solvent Yellow 98, C.I. I. Solvent Yellow 162, C.I. I. Solvent Yellow 179, C.I. I. Acid Yellow 17, C.I. I. Acid Yellow 29, C.I. I. Acid Yellow 40, C.I. I. Yellow dyes such as Acid Yellow 76.

C. I. Solvent Orange 2, C.I. I. Solvent Orange 7, C.I. I. Solvent Orange 11, C.I. I. Solvent Orange 15, C.I. I. Solvent Orange 26, C.I. I. Solvent Orange 56, C.I. I. Acid Orange 51, C.I. I. An orange dye such as Acid Orange 63.

C. I. Solvent Red 45, C.I. I. Solvent Red 49, C.I. I. Acid Red 91, C.I. I. Acid Red 92, C.I. I. Acid Red 97, C.I. I. Acid Red 114, C.I. I. Acid Red 138, C.I. I. Red dyes such as Acid Red 151.

C. I. Solvent Blue 35, C.I. I. Solvent Blue 37, C.I. I. Solvent Blue 59, C.I. I. Solvent Blue 67, C.I. I. Acid Blue 80, C.I. I. Acid Blue 83, C.I. I. Blue dyes such as Acid Blue 90.

C. I. Acid Green 9, C.I. I. Acid Green 16, C.I. I. Acid Green 25, C.I. I. Green dyes such as Acid Green 27.

In the present disclosure, the coloring material can be used alone or in combination of two or more.

The content of the coloring material with respect to the solid content of the photosensitive resin composition is not particularly limited, but is preferably 3 to 50% by weight, more preferably 5 to 30% by weight, for example. Here, the "solid content" is, for example, a component other than the above-mentioned solvent.

When a pigment is used as a coloring material in the present disclosure, it can be used together with a pigment dispersant and a pigment dispersion aid, if desired. Examples of the pigment dispersant include cationic, anionic, nonionic, and amphoteric dispersants (surfactants); polymer dispersants such as acrylic copolymers, polyesters, polyurethanes, polyethyleneimine, and polyallylamines. Can be mentioned.

Commercially available pigment dispersants can be used. For example, as an acrylic copolymer, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (all manufactured by Big Chemie (BYK)), as polyester. , Ajisper PB821, Ajisper PB822, Ajisper PB880 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), as polyurethane, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-170, Disperbyk-170 ), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), and as polyethyleneimine, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.) and the like can be mentioned.

These pigment dispersants can be used alone or in combination of two or more. The content of the pigment dispersant is usually 100 parts by weight or less, preferably 1 to 70 parts by weight, more preferably 10 to 70 parts by weight, still more preferably 30 to 60 parts by weight, based on 100 parts by weight of the pigment. .. When the content of the pigment dispersant is in the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained, which is preferable.

Examples of the pigment dispersion aid include pigment derivatives, and specific examples thereof include sulfonic acid derivatives of copper phthalocyanine, diketopyrrolopyrrole, and quinophthalone. The content of the pigment dispersion aid can be appropriately determined within a range that does not impair the object of the invention according to the present disclosure.

<Photopolymerizable compound>
In the present disclosure, the photopolymerizable compound is not particularly limited, and examples thereof include a polyfunctional vinyl compound, a polyfunctional thiol compound, and a polyfunctional epoxy compound.

The polyfunctional vinyl compound is not particularly limited as long as it is a compound having two or more vinyl groups, but for example, a di (meth) acrylate of an alkylene glycol such as ethylene glycol or propylene glycol; a polyalkylene such as polyethylene glycol or polypropylene glycol. Di (meth) acrylate of glycol; di (meth) acrylate of both-terminal hydroxylated polymers such as both-terminal hydroxypolybutadiene, both-terminal hydroxypolyisoprene, and both-terminal hydroxypolycaprilactone; glycerin, 1,2,4-butane. Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as triol, trimethylol alkane, tetramethylol alkane, pentaerythritol, dipentaerythritol; poly (meth) of polyalkylene glycol adducts of trihydric or higher polyhydric alcohols. Acrylate: Poly (meth) acrylate of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediol; polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, silicone resin (meth) Examples thereof include oligo (meth) acrylates such as acrylates. Among these, polyfunctional (meth) acrylates having two or more (meth) acryloyl groups are preferable. The polyfunctional vinyl compound can be used alone or in combination of two or more.

The polyfunctional thiol compound is not particularly limited as long as it is a compound having two or more thiol groups, and for example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, and 1,4-butanediol bis. Thioglycolate, Ethylene Glycol Bisthioglycolate, Ethylene Glycol Bisthiopropionate, Trimethylol Propantris Thiolthioglycolate, Trimethylol Propantris Thiopropionate, Trimethylol Propantris (3-mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate, pentaerythritol tetraxthiopropionate, tristrimercaptopropionate (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine, tetraethylene glycol bis3-mercaptopropionate, trimethylpropanthris 3-mercaptopropionate, tris (3-mercaptopropynyloxyethyl) Isocyanurate, pentaerythritol tetrakis 3-mercaptopropionate, dipentaerythritol tetrakis 3-mercaptopropionate, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mel) Kabutobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutylate) and the like can be mentioned. The polyfunctional thiol compound can be used alone or in combination of two or more.

The polyfunctional epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups, and for example, a glycidyl ether type epoxy compound [polyhydroxy compounds (bisphenols, polyhydric phenols, alicyclic polyhydric alcohols) , Aliper polyhydric alcohols, etc.) and glycidyl ethers produced by the reaction with epichlorohydrin (for example, (poly) C _2-4 alkylene glycols such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, etc. Diglycidyl ether; Diglycidyl ether of polyvalent phenols such as resorcin and hydroquinone; Diglycidyl ether of alicyclic polyvalent alcohols such as cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenols; bisphenols (4,4') -Bis (hydroxyphenyl) alkanes such as dihydroxybiphenyl and bisphenol A) or _{diglycidyl ether of C 2-3} alkylene oxide adduct thereof), novolac type epoxy resin (phenol novolac type or cresol novolac type epoxy resin, etc.) Etc.], glycidyl ester type epoxy compound, alicyclic epoxy compound (or cyclic aliphatic epoxy resin), heterocyclic epoxy resin (triglycidyl isocyanurate (TGIC), hydrantin type epoxy resin, etc.), glycidylamine type epoxy compound [ Reaction products of amines and epichlorohydrins, such as N-glycidyl aromatic amines {tetraglycidyl diaminodiphenylmethane (TGDDM), triglycidyl aminophenols (TGPAP, TGMAP, etc.), diglycidyl aniline (DGA), diglycidyl toluidine (DGT). ), Tetraglycidyl xylylene diamine (TGMXA, etc.), etc.}, N-glycidyl alicyclic amine (tetraglycidyl bisaminocyclohexane, etc.), etc.] and the like. The polyfunctional epoxy compound can be used alone or in combination of two or more.

The photopolymerizable compound can be used alone or in combination of two or more. The content of the photopolymerizable compound is usually 10 to 300 parts by weight, preferably 30 to 200 parts by weight, and more preferably 40 to 150 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. When the photosensitive resin composition contains a coloring material, the content of the photopolymerizable compound is usually 10 to 1000 parts by weight, preferably 50 to 600 parts by weight, based on 100 parts by weight of the coloring material. It is preferably 100 to 500 parts by weight. When the content of the photopolymerizable compound is in the above range, curing sufficiently occurs and good adhesion can be obtained.

<Photopolymerization initiator>
In the present disclosure, the photopolymerization initiator is not particularly limited, and examples thereof include a photoradical polymerization initiator and a photocationic polymerization initiator.

The photoradical polymerization initiator is a compound that generates radicals by irradiation with light to initiate a curing reaction (radical polymerization) of the photopolymerizable compound contained in the photosensitive resin composition. The photoradical polymerization initiator can be used alone or in combination of two or more.

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

Examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropyl. Examples thereof include thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl. ] -2-Methylpropane-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1 -(4-Molholinophenyl) butane-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methylbenzyl) -2-dimethyl Amino-1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethyl Amino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethyl Amino-1- (4-morpholinophenyl) -butanone, 2- (2,3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,4-dimethylbenzyl) -2-Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromobenzyl) -2-Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2-Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl)- Butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1 -(4-Molholinophenyl) -butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1-[ Examples thereof include 4- (1-methylvinyl) phenyl] propan-1-one oligomers.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl)-. 4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2) -Chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl group at 4,4'5,5'-position is carboalkoxy Examples include imidazole compounds substituted with groups.

Examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4). -Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-) Methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino) -2-Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine And so on.

Examples of the oxime compound include O-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one.

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

Examples of the benzophenone compound include benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfate, 3,3', 4,4≡-tetra (tert-). Butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. ..

The photocationic polymerization initiator is a compound that generates an acid by irradiation with light to initiate a curing reaction (cationic polymerization) of the photopolymerizable compound contained in the photosensitive resin composition, and is a cation portion that absorbs light. It consists of an anion part that is a source of acid. The photocationic polymerization initiator can be used alone or in combination of two or more.

Examples of the photocationic polymerization initiator include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salt compounds and the like. Can be mentioned.

Examples of the anion portion of the photocationic polymerization initiator include [(Y) _s B (Phf) _4-s ] ^- (in the formula, Y represents a phenyl group or a biphenylyl group. Phf has at least one hydrogen atom. perfluoroalkyl group, perfluoroalkoxy group, and .s illustrating a phenyl group substituted with at least one selected from halogen atom is an integer of _{^{0 ~ 3), BF 4 -}} , [(Rf) k PF _^6-k] - (Rf: alkyl group in which at least 80% are substituted with fluorine atoms of the hydrogen atom, k: 0 ~ 5 an _{^{_{integer), AsF 6 -, SbF 6}}} - and the like, etc. ^-, SbF ₅ OH can.

Examples of the photocationic polymerization initiator include (4-hydroxyphenyl) methylbenzyl sulfonium tetrakis (pentafluorophenyl) borate, 4- (4-biphenylylthio) phenyl-4-biphenylylphenyl sulfonium tetrakis (pentafluorophenyl). Borate, 4- (phenylthio) phenyldiphenylsulfonium phenyltris (pentafluorophenyl) borate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate, diphenyl [4 -(Phenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, diphenyl [4- (phenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, 4 -(4-Biphenylylthio) phenyl-4-biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide phenyltris (pentafluorophenyl) borate, [4- (2-Thioxanthonylthio) phenyl] Phenyl-2-thioxanthonyl sulfonium phenyltris (pentafluorophenyl) borate, 4- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate and the like can be mentioned.

Examples of the photocationic polymerization initiator include trade names "Cyracure UVI-6970", "Cyracure UVI-6974", "Cyracure UVI-6990", "Cyracure UVI-950" (manufactured by Union Carbide, USA), and "Irrage250". , "Irgacure 261", "Irgacure 264" (above, made by BASF), "CG-24-61" (made by Ciba Geigy), "Optomer SP-150", "Optomer SP-151", "Optomer SP-170", "Optomer SP-171" (above, manufactured by ADEKA Co., Ltd.), "DAICAT II" (manufactured by Daicel Co., Ltd.), "UVAC1590", "UVAC1591" (above, manufactured by Daicel Cytec Co., Ltd.), "CI-" 2064 "," CI-2739 "," CI-2624 "," CI-2481 "," CI-2734 "," CI-2855 "," CI-2823 "," CI-2758 "," CIT-1682 " (The above is manufactured by Nippon Sotatsu Co., Ltd.), "PI-2074" (manufactured by Rhodia, tetrakis (pentafluorophenyl) borate tolulucmiliodonium salt), "FFC509" (manufactured by 3M), "BBI-102", "BBI-101", "BBI-103", "MPI-103", "TPS-103", "MDS-103", "DTS-103", "NAT-103", "NDS-103" (above, Midori Chemical Co., Ltd.), "CD-1010", "CD-1011", "CD-1012" (above, manufactured by Sartomer, USA), "CPI-100P", "CPI-101A" (above, Sun Appro) Commercially available products such as (manufactured by Co., Ltd.) can be used.

The content of the photopolymerization initiator (the total amount when two or more kinds are contained) is, for example, 0.1 to 100 with respect to 100 parts by weight of the photopolymerizable compound (total amount) contained in the photosensitive resin composition. It is by weight, preferably 0.5 to 50 parts by weight, more preferably 3 to 20 parts by weight. When the content of the photopolymerization initiator is less than the above range, the curability tends to decrease. On the other hand, when the content of the photopolymerization initiator exceeds the above range, the cured product tends to be easily colored.

<Solvent>
Examples of the solvent include ether (diethyl ether; ethylene glycol mono or dialkyl ether, diethylene glycol mono or dialkyl ether, propylene glycol mono or dialkyl ether, propylene glycol mono or diaryl ether, dipropylene glycol mono or dialkyl ether, tripropylene glycol mono. Or glycol ethers such as dialkyl ether, 1,3-propanediol mono or dialkyl ether, 1,3-butanediol mono or dialkyl ether, 1,4-butanediol mono or dialkyl ether, glycerin mono, di or trialkyl ether. Such as chain ethers; cyclic ethers such as tetrahydrofuran and dioxane), esters (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, C _{5- Carous acid esters such as 6} cycloalkanediol mono or diacetate, C _5-6 cycloalkane dimethanol mono or diacetate; ethylene glycol monoalkyl ether acetate, ethylene glycol mono or diacetate, diethylene glycol monoalkyl ether acetate, diethylene glycol mono Or diacetate, propylene glycol monoalkyl ether acetate, propylene glycol mono or diacetate, dipropylene glycol monoalkyl ether acetate, dipropylene glycol mono or diacetate, 1,3-propanediol monoalkyl ether acetate, 1,3-propane Diol mono or diacetate, 1,3-butanediol monoalkyl ether acetate, 1,3-butanediol mono or diacetate, 1,4-butanediol monoalkyl ether acetate, 1,4-butanediol mono or diacetate, Glycerin mono, di or triacetate, glycerin mono or di C _1-4 alkyl ether di or monoacetate, tripropylene glycol monoalkyl ether acetate, glycol acetates such as tripropylene glycol mono or diacetate or glycol ether acetates, etc.), Examples thereof include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexene-1-one, etc.). NS. These solvents may be used alone or in combination of two or more.

In addition to the above components, the photosensitive resin composition according to the present disclosure includes, for example, resins such as novolak resin, phenol resin, imide resin, and carboxy group-containing resin, curing agents, curing accelerators, and additives (fillers, erasing agents). Contains foaming agents, flame retardants, antioxidants, UV absorbers, colorants, low stress agents, flexibility-imparting agents, waxes, resins, cross-linking agents, halogen trapping agents, leveling agents, wetting improvers, etc.) You may be.

The concentration of the alkali-soluble resin in the photosensitive resin composition according to the present disclosure is not particularly limited, but is, for example, 2 to 60% by weight, preferably 5 to 30% by weight.

Examples of the method for preparing the photosensitive resin composition of the present disclosure include a method of dissolving an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and if necessary, other additives in a solvent.

When the photosensitive resin composition of the present disclosure contains a coloring material, as a method for preparing the color material, for example, a pigment dispersant is coexisted in a solvent as necessary, and the coloring material such as a pigment is dispersed to color the color. A material dispersion is prepared, and separately, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and if necessary, other additives are dissolved in a solvent, which is mixed with the above-mentioned color material dispersion, and if necessary. Further, a method of adding a solvent and the like can be mentioned.

The photosensitive resin composition of the present disclosure is usually sealed in a container and used for distribution and storage. The photosensitive resin composition of the present disclosure is excellent in storage stability during distribution and storage.

<Cured product>
By curing the photosensitive resin composition of the present disclosure, a cured product having excellent various physical properties can be obtained. For example, the photosensitive resin composition is applied to various substrates or substrates by a conventional coating means such as a spin coater, a dip coater, a roller coater, and a slit coater to form a coating film, and then the coating film is applied. A cured product can be obtained by curing. Curing is performed, for example, by subjecting the photosensitive resin composition to light irradiation and / or heat treatment.

For the light irradiation, for example, a mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, sunlight, an electron beam source, a laser light source, an LED light source, or the like is used, and the integrated irradiation amount is, for example, 500 to 5000 mJ / cm ^2. It is preferable to irradiate in the range that becomes.

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

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

Since the cured product (coating film after curing) of the present disclosure has excellent solvent resistance and high insulating properties, a protective film (color filter protective film, etc.), an insulating film, a material for forming a microlens, etc. It is useful as.

<Color filter>
The color filter according to the present disclosure is a cured product of the photosensitive resin composition of the present disclosure. The color filter according to the present disclosure may include a coloring pattern formed from the photosensitive resin composition. The color filter can be manufactured, for example, through a step of forming a coloring pattern on a substrate using the photosensitive resin composition and a step of post-baking the coloring pattern.

As a method of forming a color filter pattern using the photosensitive resin composition of the present disclosure, for example, the photosensitive resin composition of the present disclosure is applied to a substrate or another resin layer by a conventional coating means such as a spin coater. Examples thereof include a method of coating on a surface, removing volatile components such as a solvent to form a colored layer, and exposing the colored layer through a photomask to develop the colored layer.

Examples of the substrate include a glass substrate, a silicone substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamide-imide substrate, a polyimide substrate, an Al substrate, a GaAs substrate, and the like having a flat surface. These substrates may be subjected to pretreatment such as chemical treatment with a chemical such as a silane coupling agent, plasma treatment, ion plating treatment, sputtering treatment, gas phase reaction treatment, vacuum deposition treatment and the like.

The thickness of the colored layer after drying is, for example, 0.6 to 8 μm, preferably 1 to 5 μm.

Examples of the light source of radiation used for exposure include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury lamps, argon ion lasers, and YAG lasers. Examples thereof include a laser light source such as an XeCl excimer laser and a nitrogen laser. The wavelength of radiation is preferably in the range of 190-450 nm. The exposure amount of radiation is generally preferably ^{10 to 10,000 J / m 2.}

Examples of the alkaline developer used for development include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, and 1 , 5-Diazabicyclo- [4.3.0] -5-Nonene and other aqueous solutions are preferable.

Post-baking conditions are usually about 10 to 60 minutes at 120 to 280 ° C. The film thickness of the pixels formed in this way is usually 0.5 to 5 μm, preferably 1 to 3 μm.

According to the photosensitive resin composition of the present disclosure, it is possible to obtain a coloring pattern having excellent curing reactivity and sufficient solvent resistance.

<Display device member or display device>
The display device member or display device of the present disclosure includes the above-mentioned color filter. Examples of the display device member include a color liquid crystal display element. Further, as the display device, for example, a color liquid crystal display device can be mentioned. The structure of the color liquid crystal display element or the color liquid crystal display is not particularly limited, and an appropriate structure can be adopted.

It should be noted that each aspect disclosed herein can be combined with any other feature disclosed herein. In addition, each configuration and a combination thereof in each embodiment are examples, and configurations can be added, omitted, and other changes as appropriate without departing from the gist of the present invention. The present disclosure is not limited by embodiments, but only by the scope of the claims.

Hereinafter, the present disclosure will be described in more detail based on the examples.

The weight average molecular weight (in terms of polystyrene) and the degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of the copolymer were measured under the following conditions.
Device: Detector: RID-20A (Shimadzu Corporation)
Pump: LC-20AD (Shimadzu Corporation)
System controller: CBM-20Alite (Shimadzu Corporation)
Degasser: DGU-20A3 (Shimadzu Corporation)
Auto injector: SIL-20A HT (Shimadzu Corporation)
Column: Shodex KF-806L (Showa Denko)
Eluent: THF (tetrahydrofuran) 0.8 ml / min
Temperature: Oven: 40 ° C, RI: 40 ° C
Detector: RI

The exothermic peak top temperature was measured by the following method. That is, 5 g of the copolymer-containing solution obtained in Production Examples 1 to 8 was added dropwise to 50 g of heptane with stirring. The resulting precipitate was filtered off and dried under reduced pressure to give a copolymer as a white powder. Using about 10 mg of the white powder as a sample and using a differential scanning calorimeter (DSC1 manufactured by METTLER TOLEDO), the temperature is raised from 40 ° C to 300 ° C at a rate of 5 ° C / min under a nitrogen gas atmosphere to generate heat. The peak top temperature was measured.

[Reference Example 1 / Preparation of Monomer B1]
42.4 g of chloride chloride in a mixed solution of 33.7 g of 5-norbornene-2-methanol, 41.3 g of triethylamine, and 6.5 mg of methquinone in 57.2 g of THF (tetrahydrofuran). After dropping over 40 minutes while maintaining the internal temperature at 20 ° C. or lower, the mixture was stirred at 20 ° C. for 4 hours. After confirming the disappearance of the raw material 5-norbornene-2-methanol by gas chromatography, 100 g of ether acetate and 84.0 g of water were added. After the liquid separation, the mixture was washed with 94.8 g of 10% aqueous sodium hydroxide solution and 68.0 g of water three times. The obtained organic phase was concentrated under the conditions of 40 ° C. and 15 Torr to obtain 48.3 g of a crude product of 5-norbornene-2-methylacrylate. The crude product had a purity of 93% and a yield of 86%.

72.3 g of mCPBA (3-chloroperbenzoic acid, 30) to a mixed solution of 47.5 g of the 5-norbornene-2-methylacrylate crude product and 9.4 mg of methquinone added to 141 g of ethyl acetate. % Water content) was added over 1 hour while maintaining the internal temperature at 20 ° C. or lower, and then stirred at 20 ° C. for 3 hours. After confirming the disappearance of the raw materials by gas chromatography, 278 g of a 15% aqueous sodium thiosulfate solution and 141 g of ether acetate were added, and the mixture was stirred for 15 minutes. After the liquid separation, the mixture was washed with 217 g of an 8% aqueous sodium hydrogen carbonate solution and twice with 141 g of water. By concentrating the organic phase and purifying it by silica gel column chromatography, 29.4 g of 3-oxatricyclo [3.2.1.0 ^2,4 ] octane-6-ylmethylmethacrylate (hereinafter, "monomer B1"). (Sometimes referred to as) was obtained. The purity of 3-oxatricyclo [3.2.1.0 ^2,4 ] octane-6-ylmethylmethacrylate was 99%, and the yield was 71%.

[Manufacturing Example 1]
An appropriate amount of nitrogen was flowed into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to create a nitrogen atmosphere. 150 parts by weight of propylene glycol monomethyl ether acetate was placed in the flask and heated to 80 ° C. with stirring. bottom. Then, 7 parts by weight of 2,2'-azobisisobutyronitrile (AIBN) was added while rinsing with 30 parts by weight of propylene glycol monomethyl ether acetate. Then, in the flask, a mixed solution of 11 parts by weight of acrylic acid (AA) as a monomer, 89 parts by weight of the monomer B1 and 20 parts by weight of propylene glycol monomethyl ether acetate was put into the flask using a dropping pump. It was added dropwise over about 4 hours. After the dropping of the monomer was completed, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer-containing solution having a solid content of 34.6% by weight. The weight average molecular weight Mw of the produced copolymer was 19,000, and the dispersity was 3.47.

[Manufacturing Example 2]
By performing the same operation as in Production Example 1 except that 11 parts by weight of acrylic acid (AA), 79 parts by weight of monomer B1 and 10 parts by weight of styrene (ST) were used as the monomers, the solid content was obtained. A 33.8% by weight copolymer-containing solution was obtained. The weight average molecular weight Mw of the produced copolymer was 17,000, and the dispersity was 3.33.

[Manufacturing Example 3]
By performing the same operation as in Production Example 1 except that 11 parts by weight of acrylic acid (AA), 79 parts by weight of monomer B1 and 10 parts by weight of methyl methacrylate (MMA) were used as the monomers. A copolymer-containing solution having a solid content of 34.2% by weight was obtained. The weight average molecular weight Mw of the produced copolymer was 18,500, and the dispersity was 3.41.

[Manufacturing Example 4]
By performing the same operation as in Production Example 1 except that 11 parts by weight of acrylic acid (AA), 79 parts by weight of monomer B1 and 10 parts by weight of cyclohexylmaleimide (CHMI) were used as the monomers, solids were obtained. A copolymer-containing solution of 34.4% by weight was obtained. The weight average molecular weight Mw of the produced copolymer was 18,000, and the dispersity was 3.40.

[Manufacturing Example 5]
By performing the same operation as in Production Example 1 except that 11 parts by weight of acrylic acid (AA), 79 parts by weight of monomer B1 and 10 parts by weight of N-vinylpyrrolidone (VP) were used as the monomers. , A copolymer-containing solution having a solid content of 34.4% by weight was obtained. The weight average molecular weight Mw of the produced copolymer was 17,500, and the dispersity was 3.38.

[Manufacturing Example 6]
An appropriate amount of nitrogen was flowed into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 150 parts by weight of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 65 ° C. with stirring. Then, 14 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added while rinsing with 30 parts by weight of propylene glycol monomethyl ether acetate. Next, in the flask, 11 parts by weight of acrylic acid (AA), 79 parts by weight of glycidyl methacrylate (GMA), and 10 parts by weight of methyl methacrylate (MMA) were added as monomers to 20 parts by weight of propylene glycol monomethyl ether. The solution dissolved in acetate was added dropwise over about 4 hours using a dropping pump. After the dropping of the monomer was completed, the mixture was kept at the same temperature for about 4 hours and then cooled to room temperature to obtain a copolymer-containing solution having a solid content of 33.8% by weight. The weight average molecular weight Mw of the produced copolymer was 16,000, and the dispersity was 3.32.

[Manufacturing Example 7]
Production Examples except that 11 parts by weight of acrylic acid (AA), 79 parts by weight of 3,4-epoxycyclohexylmethylmethacrylate (Cyclomer M100), and 10 parts by weight of methyl methacrylate (MMA) were used as the monomers. The same operation as in No. 6 was carried out to obtain a copolymer-containing solution having a solid content of 33.4% by weight. The weight average molecular weight Mw of the produced copolymer was 16,000, and the dispersity was 3.30.

[Manufacturing Example 8]
11 parts by weight acrylic acid (AA) as a monomer, 89 parts by weight 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-ylacrylate and 3,4-epoxytri The same operation as in Production Example 1 was carried out except that a mixture of cyclo [5.2.1.0 ^2,6 ] decan-8-ylacrylate (monomer B2) was used, and the solid content was 34.1% by weight. A polymer-containing solution was obtained. The weight average molecular weight Mw of the produced copolymer was 18,000, and the dispersity was 3.43.

Table 1 shows the copolymer composition, the weight average molecular weight of the copolymer, the degree of dispersion, and the exothermic peak top temperature in Production Examples 1 to 8.

[Example 1-1]
The copolymer obtained in Production Example 1 as an alkali-soluble resin was 8.09 g as a copolymer-containing solution, 2.25 g as a photopolymerizable compound, and 0.20 g as a photopolymerization initiator. , MMPGAC (6.83 g) as a polymer was weighed into a container and stirred for 30 minutes to prepare a photosensitive resin composition 1-1.

[Example 1-2]
The same operation as in Example 1-1 was carried out except that 8.09 g of the copolymer obtained in Production Example 2 was used as the alkali-soluble resin as the copolymer-containing solution, and the photosensitive resin composition 1-2 was carried out. Was prepared.

[Example 1-3]
The same operation as in Example 1-1 was carried out except that 8.09 g of the copolymer obtained in Production Example 3 was used as the alkali-soluble resin as the copolymer-containing solution, and the photosensitive resin composition 1-3 was performed. Was prepared.

[Example 1-4]
The same operation as in Example 1-1 was carried out except that 8.09 g of the copolymer obtained in Production Example 4 was used as the alkali-soluble resin as the copolymer-containing solution, and the photosensitive resin composition 1-4 Was prepared.

[Example 1-5]
The same operation as in Example 1-1 was carried out except that 8.09 g of the copolymer obtained in Production Example 5 was used as the alkali-soluble resin as the copolymer-containing solution, and the photosensitive resin composition 1-5 was carried out. Was prepared.

[Comparative Example 1-1]
The same operation as in Example 1-1 was carried out except that 8.09 g of the copolymer obtained in Production Example 6 was used as the alkali-soluble resin as the copolymer-containing solution, and the photosensitive resin composition 1-6 was carried out. Was prepared.

[Comparative Example 1-2]
The same operation as in Example 1-1 was carried out except that 8.09 g of the copolymer obtained in Production Example 7 was used as the alkali-soluble resin as the copolymer-containing solution, and the photosensitive resin composition 1-7 was carried out. Was prepared.

[Comparative Example 1-3]
The same operation as in Example 1-1 was carried out except that 8.09 g of the copolymer obtained in Production Example 8 was used as the alkali-soluble resin as the copolymer-containing solution, and the photosensitive resin composition 1-8 was carried out. Was prepared.

Table 2 shows the compositions of the photosensitive resin compositions of the above Examples and Comparative Examples.

[Example 2-1]
C.I. I. 7.7 g of Pigment Red 254, 3.1 g of DISPERBYK-2000 as a dispersant, and 36.0 g of MMPGAC as a solvent were weighed into a container, and 45 g of zirconia beads having a diameter of 1.0 mm were added and covered. This was shaken with a paint shaker for 3 hours, and after 3 hours, the pigment dispersion and the zirconia beads were separated, 45 g of 0.5 mm zirconia beads were added, and the mixture was shaken with a paint shaker for another 3 hours. Then, the pigment dispersion liquid and the zirconia beads were separated, 45 g of 0.3 mm zirconia beads were added, and the mixture was further shaken with a paint shaker for 3 hours, and then the zirconia beads were separated to obtain a pigment dispersion liquid.
With respect to 4.68 g of the obtained pigment dispersion, 8.09 g of the copolymer obtained in Production Example 1 as an alkali-soluble resin, 2.25 g of DPHA as a photopolymerizable compound, and light A photosensitive resin composition 2-1 was prepared by weighing 0.20 g of 1-hydroxycyclohexylphenyl ketone as a polymerization initiator and 15.2 g of MMPGAC as a solvent in a container and stirring for 30 minutes.

[Example 2-2]
The same operation as in Example 2-1 was carried out except that 8.09 g of the copolymer obtained in Production Example 2 was used as the alkali-soluble resin as the copolymer-containing solution, and the photosensitive resin composition 2 was subjected to the same operation. -2 was prepared.

[Example 2-3]
The same operation as in Example 2-1 was carried out except that 8.09 g of the copolymer obtained in Production Example 3 was used as the alkali-soluble resin as the copolymer-containing solution, and the photosensitive resin composition 2 was subjected to the same operation. -3 was prepared.

[Example 2-4]
The same operation as in Example 2-1 was carried out except that 8.09 g of the copolymer obtained in Production Example 4 was used as the alkali-soluble resin as the copolymer-containing solution, and the photosensitive resin composition 2 was subjected to the same operation. -4 was prepared.

[Example 2-5]
The same operation as in Example 2-1 was carried out except that 8.09 g of the copolymer obtained in Production Example 5 was used as the alkali-soluble resin as the copolymer-containing solution, and the photosensitive resin composition 2 was subjected to the same operation. -5 was prepared.

[Comparative Example 2-1]
The same operation as in Example 2-1 was carried out except that 8.09 g of the copolymer obtained in Production Example 6 was used as the alkali-soluble resin as the copolymer-containing solution, and the photosensitive resin composition 2 was subjected to the same operation. -6 was prepared.

[Comparative Example 2-2]
The same operation as in Example 2-1 was carried out except that 8.09 g of the copolymer obtained in Production Example 7 was used as the alkali-soluble resin as the copolymer-containing solution, and the photosensitive resin composition 2 was subjected to the same operation. -7 was prepared.

[Comparative Example 2-3]
The same operation as in Example 2-1 was carried out except that 8.09 g of the copolymer obtained in Production Example 8 was used as the alkali-soluble resin as the copolymer-containing solution, and the photosensitive resin composition 2 was subjected to the same operation. -8 was prepared.

Table 4 shows the compositions of the photosensitive resin compositions of the above Examples and Comparative Examples.

<Evaluation test>
The following evaluation tests were carried out using the photosensitive resin compositions obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3. The results are shown in Table 3.

(1) Storage stability test-1
The photosensitive resin compositions obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3 were stored in an oven at 40 ° C. for 1 week. The viscosity immediately after polymerization and the viscosity after storage at 40 ° C. for 1 week were measured. The viscosity increase rate was calculated by the following formula. The viscosity (unit: mPa · s) was measured using a viscometer (trade name “LVDV2T”, manufactured by Brookfield) under the conditions of a rotation speed of 60 and a temperature of 23 ° C.
P: Viscosity immediately after polymerization, Q: Viscosity after storage at 40 ° C. for 1 week Viscosity increase rate = {(Q / P) x 100} -100

(2) Solvent resistance test-1
The photosensitive resin compositions obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3 are applied to a glass plate with a spin coater, and then heat-cured at 200 ° C. for 30 minutes for testing. Pieces were made. The thickness of the coating film after curing was 3 μm.

One drop each of γ-butyrolactone (γ-BL) and N-methylpyrrolidone (NMP) was added dropwise to the test piece, and the mixture was left for 10 minutes. After that, wash with water, and if the part where the solvent is dropped has not changed at all ◎, a slight trace of the solvent remains, but if it disappears if wiped off ○, if the trace of the solvent remains, it does not seem to disappear even if wiped off If it is △, if it is completely discolored, it is marked as ×.

(3) Solvent resistance test-2
In the preparation of the test piece, the solvent resistance test of the cured product was carried out in the same manner as in the solvent resistance test-1 except that the curing temperature was set to 230 ° C.

The photosensitive resin compositions of Examples 1-1 to 1-5 were difficult to thicken even at 40 ° C. and had good storage stability. Further, even when the curing temperature was 200 ° C., good solvent resistance was exhibited as in the case of 230 ° C. On the other hand, it was found that the photosensitive resin compositions of Comparative Examples 1-1 to 1-2 had poor storage stability as can be understood from the fact that they gel at 40 ° C. Further, although the photosensitive resin composition of Comparative Example 3 has good storage stability by using the monomer B2 (EDCPA), it does not sufficiently cure when the curing temperature is lowered from 230 ° C. to 200 ° C., so that it is resistant to curing. It was found that the solvent property was reduced.

Next, the following evaluation tests were conducted using the photosensitive resin compositions obtained in Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-3. The results are shown in Table 5.

(1) Storage stability test-2
The photosensitive resin compositions obtained in Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-3 were stored in an oven at 40 ° C. for 1 week. The viscosity immediately after polymerization and the viscosity after storage at 40 ° C. for 1 week were measured. The viscosity increase rate was calculated by the following formula. The viscosity (unit: mPa · s) was measured using a viscometer (trade name “LVDV2T”, manufactured by Brookfield) under the conditions of a rotation speed of 60 and a temperature of 23 ° C.
P: Viscosity immediately after polymerization, Q: Viscosity after storage at 40 ° C. for 1 week Viscosity increase rate = {(Q / P) x 100} -100

(2) Solvent resistance test-3
The photosensitive resin compositions obtained in Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-3 are applied to a glass plate with a spin coater, and then heat-cured at 200 ° C. for 30 minutes for testing. Pieces were made. The thickness of the coating film after curing was 2 μm.

(3) Solvent resistance test-4
In the preparation of the test piece, the solvent resistance test of the cured product was carried out in the same manner as in the solvent resistance test-3 except that the curing temperature was set to 230 ° C.

The photosensitive resin compositions of Examples 2-1 to 2-5 were difficult to thicken even at 40 ° C. and had good storage stability. Further, even when the curing temperature was 200 ° C., good solvent resistance was exhibited as in the case of 230 ° C. On the other hand, it was found that the photosensitive resin compositions of Comparative Examples 2-1 to 2-2 had poor storage stability as can be understood from the fact that they thickened at 40 ° C. Further, although the photosensitive resin composition of Comparative Example 2-3 has good storage stability by using the monomer B2 (EDCPA), it is not sufficiently cured when the curing temperature is lowered from 230 ° C. to 200 ° C. , It was found that the solvent resistance was lowered.

The components used in Production Examples, Examples and Comparative Examples will be described below.
Monomer B1: 3-oxatricyclo [3.2.1.0 ^2,4 ] octane-6-ylmethylmethacrylate (see Reference Example 1)
GMA: Glycidyl methacrylate (manufactured by NOF CORPORATION)
Cyclomer M100: 3,4-epoxycyclohexylmethylmethacrylate (manufactured by Daicel Corporation)
Monomer B2: 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane- Mixture of 8-yl acrylate (trade name "E-DCPA", manufactured by Daicel Corporation)
ST: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
CHMI: Cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.)
VP: N-vinylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.)
MMPGAC: Propylene glycol monomethyl ether acetate (manufactured by Daicel Corporation)
PR 254: C.I. I. Pigment Red 254 (manufactured by Tokyo Chemical Industry Co., Ltd.)
DISPERBYK-2000: Amine value 4 mgKOH / g, non-volatile content 40% (manufactured by Big Chemie Japan)
DHPA: Dipentaerythritol hexaacrylate (trade name "KAYARAD DPHA"; manufactured by Nippon Kayaku Co., Ltd.)
1-Hydroxycyclohexylphenyl ketone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

As a summary of the above, the configuration of the present invention and variations thereof will be added below.
[1]
Contains an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.
The alkali-soluble resin has a structural unit (A) derived from an unsaturated carboxylic acid or an anhydride thereof, and the above formula (1) (in the formula, R ¹ and R ² have the same or different hydrogen atoms or carbon, respectively. It represents an alkyl group of numbers 1 to 7. X represents a divalent hydrocarbon group which may contain a single bond or a hetero atom. Y has an alkyl group having 1 to 3 carbon atoms as a substituent. A structural unit (B) derived from a compound represented by a compound represented by a methylene group or an ethylene group, an oxygen atom, or a sulfur atom which may be bonded to an oxygen atom. N represents an integer of 0 to 7). A photosensitive resin which is a copolymer containing and has a peak top temperature of 180 to 220 ° C. that appears when the temperature is raised at a rate of 5 ° C./min using a differential scanning calorimeter. Composition.
[2]
The compound represented by the formula (1) is the same as that described in the formula (1a) (in the formula, R ¹ , R ² , X, Y, and n). The photosensitive resin composition according to [1], which is a compound represented by (.).
[3]
The photosensitive according to [1] or [2], wherein the copolymer further contains a structural unit (C) derived from at least one compound selected from the group consisting of the following (c1) to (c4). Resin composition.
(C1) A styrene (c2) N-substituted maleimide (c3) N-vinyl compound (c4) which may be substituted with an alkyl group. The above formula (2) (in the formula, R ¹¹ is a hydrogen atom or 1 to 7 carbon atoms. ^{R 12} represents a hydrocarbon group which may contain a hetero atom. Z represents a hetero atom), which is an unsaturated carboxylic acid derivative [4].
The photosensitive resin composition according to any one of [1] to [3], wherein the copolymer further contains a structural unit derived from (meth) acrylamide or (meth) acrylonitrile as the structural unit (D). thing.
[5]
Any of [1] to [4], wherein the ratio of the structural unit (A) to all the structural units of the copolymer is 2 to 60% by weight, 3 to 40% by weight, or 5 to 20% by weight. The photosensitive resin composition according to the above.
[6]
Any of [1] to [5], wherein the ratio of the structural unit (B) to all the structural units of the copolymer is 40 to 98% by weight, 60 to 95% by weight, or 75 to 90% by weight. The photosensitive resin composition according to the above.
[7]
The ratio of the structural unit (C) to all the structural units of the copolymer is 0 to 85% by weight, 1 to 60% by weight, and 2 to 40% by weight, [3], [5], and [6]. The photosensitive resin composition according to any one of.
[8]
The ratio of the structural unit (A) to all the structural units of the copolymer is 2 to 60% by weight, the content of the structural unit (B) is 40 to 98% by weight, and the content of the structural unit (C) is 0 to 0 to. The photosensitive resin composition according to any one of [3], [5] to [7], which is 85% by weight.
[9]
When the copolymer contains the structural unit (A) and the structural unit (B) and does not include the structural unit (C), the total amount of the structural unit (A) and the structural unit (B) is the total structural unit. On the other hand, it is 90% by weight or more, 95% by weight or more, 99% by weight or more, or substantially 100% by weight, and the copolymer is a constituent unit (A), a constituent unit (B), and a constituent unit (C). When the above is included, the total amount of the structural units (A) to (C) is 90% by weight or more, 95% by weight or more, 99% by weight or more, or 100% by weight with respect to all the structural units, [1] to [ 8] The photosensitive resin composition according to any one of.
[10]
The photosensitive resin composition according to any one of [1] to [9], wherein the weight average molecular weight (Mw) of the copolymer is 1000 to 1000000, 3000 to 300,000, or 5000 to 100,000.
[11]
The molecular weight distribution of the copolymer (ratio of weight average molecular weight to number average molecular weight: Mw / Mn) is 5.0 or less, 1.0 to 4.5, or 1.0 to 4.0. 1] The photosensitive resin composition according to any one of [10].
[12]
Described in any one of [1] to [11], wherein the exothermic peak top temperature that appears when the polymer is heated at a rate of 5 ° C./min using a differential scanning calorimeter is 180 to 220 ° C. Photosensitive resin composition.
[13]
The photosensitive resin composition according to any one of [1] to [12], further comprising a coloring material.
[14]
The photosensitive resin composition according to [13], wherein the coloring material is a pigment and / or a dye.
[15]
The photosensitive resin composition according to [13] or [14], wherein the content of the coloring material with respect to the solid content of the photosensitive resin composition is 3 to 50% by weight and 5 to 30% by weight.
[16]
The photosensitive compound according to any one of [1] to [15], wherein the photopolymerizable compound contains at least one selected from the group consisting of a polyfunctional vinyl compound, a polyfunctional thiol compound, and a polyfunctional epoxy compound. Resin composition.
[17]
The content of the photopolymerizable compound is 10 to 300 parts by weight, 30 to 200 parts by weight, or 40 to 150 parts by weight with respect to 100 parts by weight of the alkali-soluble resin, and the photosensitive resin composition contains a coloring material. In the case of [1] to [16], the content of the photopolymerizable compound is 10 to 1000 parts by weight, 50 to 600 parts by weight, or 100 to 500 parts by weight with respect to 100 parts by weight of the coloring material. The photosensitive resin composition according to any one.
[18]
A cured product of the photosensitive resin composition according to any one of [1] to [17].
[19]
A color filter which is a cured product of the photosensitive resin composition according to any one of [1] to [17].
[20]
A display device member or display device including the color filter according to [19].

Claims

Contains an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.
The alkali-soluble resin contains a structural unit (A) derived from an unsaturated carboxylic acid or an anhydride thereof, and the following formula (1).

(In the formula, R 1 and R 2 are the same or different, respectively, and represent a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. X is a divalent hydrocarbon group which may contain a single bond or a hetero atom. Y represents a methylene group or an ethylene group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom which may be bonded to an oxygen atom. N is 0. Indicates an integer of ~ 7.)
It is a copolymer containing the structural unit (B) derived from the compound represented by, and the exothermic peak top temperature that appears when the temperature is raised at a rate of 5 ° C./min using a differential scanning calorimeter is 180. A photosensitive resin composition that is a copolymer at ~ 220 ° C.
The photosensitive resin composition according to claim 1, wherein the copolymer further comprises a structural unit (C) derived from at least one compound selected from the group consisting of the following (c1) to (c4).
(C1) Styrene (c2) N-substituted maleimide (c3) N-vinyl compound (c4) which may be substituted with an alkyl group The following formula (2)

(In the formula, R 11 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R 12 represents a hydrocarbon group which may contain a hetero atom. Z represents a hetero atom.)
Unsaturated carboxylic acid derivative represented by
The ratio of the structural unit (A) to all the structural units of the copolymer is 2 to 60% by weight, the ratio of the structural unit (B) is 40 to 98% by weight, and the ratio of the structural unit (C) is 0 to 0 to. The photosensitive resin composition according to claim 2, which is 85% by weight.
The photosensitive resin composition according to any one of claims 1 to 3, further comprising a coloring material.
The photosensitive resin composition according to claim 4, wherein the coloring material is a pigment and / or a dye.
A cured product of the photosensitive resin composition according to any one of claims 1 to 5.
A color filter which is a cured product of the photosensitive resin composition according to any one of claims 1 to 5.
A display device member or display device including the color filter according to claim 7.