WO2018235664A1

WO2018235664A1 - Polymerizable composition, photosensitive composition for black matrixes, and photosensitive composition for black column spacers

Info

Publication number: WO2018235664A1
Application number: PCT/JP2018/022276
Authority: WO
Inventors: 桂典松平; 翔六谷; 祐也中田
Original assignee: 株式会社Adeka
Priority date: 2017-06-20
Filing date: 2018-06-11
Publication date: 2018-12-27
Also published as: JPWO2018235664A1; KR102597826B1; JP7218069B2; CN110520796A; TWI778082B; TW201906874A; KR20200021044A

Abstract

A polymerizable composition according to the present invention is a polymerizable composition containing a polymerization initiator (A), a coloring agent (B), an alkali-developable compound (C) and an ethylenically unsaturated compound (D) excluding the alkali-developable compound (C), wherein the polymerization initiator (A) includes an α-aminoacetophenone compound (A1) having a hydroxyl group. It is preferred that the polymerization initiator (A) also includes an oxime ester compound (A2) having a group represented by general formula (I) in addition to the α-aminoacetophenone compound (A1) having a hydroxyl group. (With respect to the definitions for the symbols in the formula, see the description.)

Description

Polymerizable composition, photosensitive composition for black matrix, and photosensitive composition for black column spacer

The present invention relates to a polymerizable composition containing an α-aminoacetophenone compound having a hydroxyl group as a polymerization initiator, and further containing an ethylenic unsaturated compound excluding a coloring agent, an alkali developable compound and an alkali developable compound. The present invention also relates to a photosensitive composition for a black matrix (hereinafter also described as BM) containing this composition, a photosensitive composition for a black column spacer (hereinafter also described as BCS), and a cured composition obtained from these compositions Related to things.

In display devices such as liquid crystal display devices and organic EL display devices, a spacer is used to maintain the distance between the upper and lower substrates of the cell.

The spacer is formed by applying the polymerizable composition to the substrate, exposing it through a predetermined mask and developing it. In recent years, BCS has been used that integrates a column spacer and a black matrix into one module and has a light shielding property.

Patent Document 1 describes a photopolymerization initiator for a photosensitive solder resist containing an α-aminoalkylphenone compound. Patent Document 2 describes a photosensitive resin composition for BCS formation which can form a BCS having a low relative dielectric constant, which contains carbon black subjected to a treatment for introducing an acidic group. Patent Document 3 can form a BCS showing a good elastic recovery, containing a copolymer, an epoxy resin compound or a compound derived therefrom, and a colorant containing a black colorant and a blue colorant. A colored photosensitive resin composition is described.

JP, 2016-090857, A JP, 2015-093986, A JP, 2014-146029, A

The problem to be solved by the present invention is that there has been no cured product (especially BCS) which is excellent in elastic recovery, light shielding property, chemical resistance, low in dielectric constant and good in electric characteristics.

Accordingly, the object of the present invention is to provide a polymerizable composition which is excellent in elastic recovery, light shielding property and chemical resistance, has a low dielectric constant and has a good electrical property, a photosensitive composition for BM and a photosensitive for BCS. It is providing a sex composition. The present invention also provides the polymerizable composition, the photosensitive composition for the BM, a cured product obtained from the photosensitive composition for the BCS, a display device containing the cured product, and a method for producing the cured product. It is.

The present invention achieves the above object by providing the following [1] to [9] after earnest study.

[1] A polymerizable composition containing a polymerization initiator (A), a colorant (B), an alkali developable compound (C) and an ethylenically unsaturated compound (D) excluding the alkali developable compound (C) There,
A polymerizable composition, wherein the polymerization initiator (A) contains an α-aminoacetophenone compound (A1) having a hydroxyl group.

[2] The polymerizable composition according to [1], wherein the polymerization initiator (A) is a polymerization initiator further containing an oxime ester compound (A2) having a group represented by the following general formula (I) .

(Wherein, R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocycle) Represents
The hydrogen atom in the group represented by R ¹ and R ² is a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, It may be substituted with an isocyanate group or a group having 2 to 20 carbon atoms containing a heterocycle, and the methylene group in the groups represented by R ¹ and R ² is —O—, —CO—, —COO— ^{^{, -OCO -, - NR 3 -}} , - NR 3 CO -, - S -, - CS -, - SO 2 -, - SCO -, - COS -, - OCS-, substituted with an unsaturated bond or CSO- In some cases,
R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
m represents 0 or 1;
* In the formula represents a bond. )

[3] The polymerizable composition according to [1] or [2], wherein the colorant (B) is a black pigment.

[4] The polymerizable composition according to any one of [1] to [3], wherein the alkali developable compound (C) is an alkali developable compound represented by the following general formula (II).

(Wherein, R ¹¹ , R ¹³ and R ¹⁵ each independently represent a hydrogen atom or a methyl group, and R ¹² , R ¹⁴ and R ¹⁶ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a complex) Represents a group having 2 to 20 carbon atoms containing a ring,
When a plurality of R ¹³ and R ¹⁴ exist, they may be the same or different,
Y ¹ , Y ² and Y ^{3 each} represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocycle,
When ^two or more Y ² exist, they may be the same or different,
Z ¹ , Z ² and Z ^{3 each} represent a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
When ^two or more Z ² exist, they may be the same or different,
The hydrogen atom in the group represented by R ¹² , R ¹⁴ , R ¹⁶ , Y ¹ , Y ² , Y ³ , Z ¹ , Z ² and Z ³ is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, It may be substituted by a group containing a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a mercapto group, an isocyanate group or a heterocycle, and R ¹² , R ¹⁴ , R ¹⁶ , Y ¹ , Y ² , The methylene group in the group represented by Y ³ , Z ¹ , Z ² and Z ³ is —O—, —CO—, —COO—, —OCO—, —S—, —SO ₂ —, —SCO— or May be replaced with -COS-,
n represents a positive number of 0 or 10 or less, a represents a positive number of 0 or 4 or less, b represents a positive number of 0 or 3 or less, and c is a positive number of 0 or 4 or less And when n is 2 or more, b may be the same or different. )

[5] A photosensitive composition for black matrix comprising the polymerizable composition according to any one of [1] to [4].

[6] A photosensitive composition for a black column spacer, comprising the polymerizable composition according to any one of [1] to [4].

[7] The polymerizable composition according to any one of [1] to [4], the photosensitive composition for a black matrix according to [5], and the photosensitive composition for a black column spacer according to [6] Method of producing a cured product by light irradiation or heating using a product.

[8] The polymerizable composition according to any one of [1] to [4], the photosensitive composition for a black matrix according to [5], or the photosensitive composition for a black column spacer according to [6] Cured product.

[9] A display device containing the cured product according to [8].

Hereinafter, the polymerizable composition of the present invention will be described in detail based on preferred embodiments.

The polymerizable composition of the present invention contains, as a polymerization initiator, an α-aminoacetophenone compound having a hydroxyl group, a colorant, an alkali developable compound and an ethylenically unsaturated compound other than the alkali developable compound. Hereinafter, each component will be described in order.

<Polymerization initiator (A)>
The polymerization initiator (A) used in the polymerizable composition of the present invention contains a hydroxyl group-containing α-aminoacetophenone compound (A1) [hereinafter, also described as the component (A1)], and the conventionally known component (A1) It is possible to use a radical polymerization initiator other than.

The said radical polymerization initiator is a photo radical polymerization initiator and a thermal radical polymerization initiator. A photo radical polymerization initiator is more preferable because of high reactivity.

The photo radical polymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and conventionally known compounds can be used. For example, acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone Preferred are compounds based on the compound and oxime ester compounds and the like.

The component (A1) means a compound having a hydroxyl group and an α-aminoacetophenone structure in one molecule, and is not particularly limited, but preferably includes a compound represented by the following general formula (V).

(Wherein, Xr represents a structure represented by the following general formula (i), (ii) or (iii),
Xs represents a sulfur atom or NR ¹⁰⁰ ,
R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an arylalkyl group having 7 to 20 carbon atoms, or the number of carbon atoms And the alkyl group may be substituted with a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group, and the phenyl group and the arylalkyl group each have 1 to 4 carbon atoms. In some cases substituted with an alkyl group, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group,
R ¹⁰¹ and R ¹⁰² may form a heterocyclic ring linked to 3-6 membered ring, the nitrogen atom in the heterocyclic ring may R ⁹⁹ is bonded R ¹⁰³ and R ¹⁰⁴ may be linked to form a 3- to 6-membered ring,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group or an alkyl group having 1 to 12 carbon atoms, and the alkyl group is It may be substituted by a halogen atom, a carboxyl group, a cyano group, a nitro group or a hydroxyl group,
R ⁹⁹ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an arylalkyl group having 7 to 20 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, and the alkyl group is a hydroxyl group or a carboxyl group , And may be substituted with a halogen atom, a cyano group or a nitro group, and the phenyl group and the arylalkyl group are each an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group May be replaced by
Methylene groups in each alkyl group and each aryl alkyl groups listed above, -O -, - S -, - NR 117 -, - CO -, - CO-O -, - O-CO- or -O It may be substituted by -CO-O-.
R ¹¹⁷ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an arylalkyl group having 7 to 20 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, and the alkyl group is a hydroxyl group or a carboxyl group The phenyl group and the arylalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group. It may be substituted by a group.
However, the compound represented by Formula (V) has at least one hydroxyl group in the molecule. )

(Wherein, each of R ¹⁰⁹ and R ¹¹⁰ independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and even when p is 2 or more, they are the same) It may be different,
Following in the formula (i-1)

In methylene groups represented by structure is, -O -, - S -, - NR 117, -CO -, - CO-O -, - O-CO- or -O-CO-O- in substituted May be
R ¹¹¹ represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, an amino group or a phenyl group, and the phenyl group is an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group And p may be substituted with a nitro group, and p represents a number of 1 to 12. )

(Wherein, R ¹¹² , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ and R ¹¹⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group or an alkyl group having 1 to 12 carbon atoms, alkyl group may have been substituted by a halogen atom, a cyano group, a nitro group or a hydroxyl group, a methylene group in the alkyl group, -O -, - S -, - NR 117, -CO -, - CO- It may be substituted by O-, -O-CO- or -O-CO-O-, and R ¹⁰⁶ or R ¹⁰⁷ may combine with R ¹¹² or R ¹¹⁶ to form a ring. .)

(Wherein, R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ are the same as the above general formula (V), and R ¹⁰⁹ , R ¹¹⁰ and p are the above The same as general formula (i).)

Examples of the alkyl group having 1 to 12 carbon atoms described above as the explanation of the general formula (V) include, for example, a carbon atom which is an example of a hydrocarbon group having 1 to 20 carbon atoms in the following general formula (I) Among the alkyl groups of 1 to 20, those having 1 to 12 carbon atoms can be mentioned.

Examples of the alkyl group having 1 to 4 carbon atoms described above as the explanation of the general formula (V) include 1 to 20 carbon atoms which is an example of a hydrocarbon group having 1 to 20 carbon atoms in the following general formula (I) Among the groups described below as the alkyl group of -20, one having 1 to 4 carbon atoms can be mentioned.

Examples of the arylalkyl group having 7 to 20 carbon atoms described above as the explanation of the general formula (V) include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like.

As the alkenyl group having 2 to 12 carbon atoms described above as the explanation of the general formula (V), a vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group And groups such as 3-butenyl group, 1-octenyl group and 1-decenyl group.

Preferred examples of the 3- to 6-membered heterocyclic ring which may be formed by linking R ¹⁰¹ and R ¹⁰² in the general formula (V) include piperidine ring, piperazine ring, morpholine ring, lactam ring and the like.

Preferred examples of the 3- to 6-membered ring which can be formed by linking R ¹⁰³ and R ¹⁰⁴ in the general formula (V) include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a lactone ring and a lactam ring. .

Examples of the ring formed by combining R ¹⁰⁶ or R ¹⁰⁷ with R ¹¹² or R ^{116 in the} general formula (V) include a carbazole ring, a tianthrene ring and a dibenzothiophene ring as a structure combined with the benzene ring on both sides of Xs. It can be mentioned.

Examples of each halogen atom described above as an explanation in the general formula (V) include fluorine, chlorine, bromine and iodine.

Examples of preferable component (A1) include the following compound Nos. A1-1 to A-11.

Examples of the acetophenone-based compound other than the component (A1) include α-aminoacetophenone compounds and α-hydroxyacetophenone compounds having no hydroxyl group.

Examples of acetophenone compounds other than the component (A1) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone , 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tert-butyl dichloroacetophenone, p-tert-butyl trichloro Acetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -bu Non-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl -1-propan-1-one and the like.

Examples of the benzyl compound include benzyl and the like.

Examples of benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide. .

Examples of thioxanthone compounds include thioxanthone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone and the like.

Examples of oxime ester compounds include oxime ester compounds (A2) having a group represented by the above general formula (I), etc. Among the above photo radical polymerization initiators, high sensitivity can be obtained by using in combination with the component (A1). As a result, it can be preferably used in the polymerizable composition of the present invention.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ³ in the general formula (I) is not particularly limited, but is preferably an alkyl group having 1 to 20 carbon atoms, An alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyl alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or 7 to 20 carbon atoms Represents an arylalkyl group or the like. As the sensitivity when used as a polymerization initiator (A) is good, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, carbon More preferred is a cycloalkylalkyl group having 4 to 10 atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 10 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl and isooctyl. 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and icosyl and the like. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl and isooctyl. 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl and the like.

Examples of the above alkenyl group having 2 to 20 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, and the like. -Heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl, and 4 , 8, 12-tetradecatrienyl allyl and the like. Examples of the above alkenyl groups having 2 to 10 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, and the like -Heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl and the like.

The above-mentioned cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo [1.1.1] pentanyl and tetradecahydroanthracenyl etc. It can be mentioned. Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene and bicyclo [1. 1.1] Pentanyl and the like.

The above-mentioned cycloalkyl alkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which the hydrogen atom of the alkyl group is substituted with a cycloalkyl group. For example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2- Cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-Cyclononylpropyl, 3-Cyclodecylpropyl, 4-Cyclobutylbutyl, 4-Cyclopentylbutyl, 4-Cyclohexylbutyl, 4-Cycloheptylbutyl, 4-CyclooctylB Le, 4-cyclopropyl-nonyl-butyl, 4-cyclopropyl-decyl-butyl, 3-3-adamantyl propyl and deca hydro-naphthylpropyl and the like. Examples of the above cycloalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, 2-cyclobutylethyl, -Cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4 And -cyclopentylbutyl and 4-cyclohexylbutyl and the like.

Examples of the aryl group having 6 to 20 carbon atoms include one or more of phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl and the like, the above alkyl group, the above alkenyl group, carboxyl group, halogen atom and the like Substituted phenyl, biphenylyl, naphthyl, anthryl and the like, for example, 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl and the like can be mentioned. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl and naphthyl and the like, and phenyl substituted with one or more of the above alkyl group, the above alkenyl group, carboxyl group, halogen atom and the like. And biphenylyl, naphthyl, anthryl and the like, for example, 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl and the like.

The above-mentioned arylalkyl group having 7 to 20 carbon atoms means 7 to 20 in which the hydrogen atom of the alkyl group is replaced with an aryl group having 6 to 19 carbon atoms among the above-mentioned aryl groups having 6 to 20 carbon atoms. Means a group having two carbon atoms. For example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and naphthylpropyl and the like can be mentioned. The arylalkyl group having 7 to 10 carbon atoms is exemplified by 7 to 10 in which a hydrogen atom of the alkyl group is replaced with an aryl group having 6 to 9 carbon atoms among the aryl groups having 6 to 20 carbon atoms. Means a group having one carbon atom, and examples thereof include benzyl, α-methylbenzyl, α, α-dimethylbenzyl and phenylethyl.

When a hydrogen atom in a group having 2 to 20 carbon atoms containing a heterocyclic ring represented by R ¹ and R ² in the general formula (I) and a group represented by R ¹ and R ² is substituted The heterocyclic group having 2 to 20 carbon atoms is not particularly limited, and examples thereof include pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, and the like. Triazyl, triazylmethyl, pyrrolidinyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl , Morpholinyl, thiomorpholinyl, 2-pyrrolidin-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxazolidin-3-yl and the like When it is specifically described including substituents and the like, groups having the following structures and the like can be mentioned.

(In the above formulae, each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z represents a direct bond or an alkylene group having 1 to 6 carbon atoms. Means that the group represented by these formulas is a bond at * part.)

Examples of the alkyl group having 1 to 6 carbon atoms represented by R in the above-mentioned formula include those having 1 to 6 carbon atoms in the above-mentioned alkyl group having 1 to 20 carbon atoms. it can.
As the alkylene group having 1 to 6 carbon atoms represented by Z in the above formula, methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 1,2-dimethylpropylene, 1 , 3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, etc. And an alkylene group of

As each halogen atom described in the notes of the general formulas (I) and (III), fluorine, chlorine, bromine and iodine can be mentioned.

In the present specification, as an unsaturated bond which may substitute a methylene group in the group described in the annotation of each of the general formulas (I) or (IV), -C = C-, -C≡C-, etc. Can be mentioned.

Among the compounds having a group represented by the above general formula (I), a compound represented by the following general formula (III) is preferably used in the polymerizable composition of the present invention since the sensitivity is particularly high.

^(Wherein, R 1, ^{R 2} and m are the same as ^R 1, ^{R 2} and m, respectively, in formula (I),
R ²¹ and R ²² each independently represent a hydrogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms Or a group having 2 to 20 carbon atoms containing a heterocycle,
X ¹ represents an oxygen atom, a sulfur atom, a selenium atom, CR ²³ R ²⁴ , CO, NR ²⁵ or PR ²⁶ ,
X ² represents non-bonding, direct bonding, a hydrocarbon group having 1 to 20 carbon atoms, CO, and R ²³ to R ²⁶ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or And a hydrogen atom in the group represented by R ²¹ to R ²⁶ is a halogen atom, a nitro group, a cyan group, a hydroxyl group, a carboxyl group or a heterocyclic group. May be replaced,
The methylene group in the groups represented by R ²¹ to R ²⁶ may be substituted by —O— or —CO— under the condition that oxygen is not adjacent to each other,
R ²¹ to R ²⁶ may independently form a ring together with either of adjacent benzene rings,
g represents a number from 0 to 4;
h represents a number of 0 to 3; )

The hydrocarbon group having 1 to 20 carbon atoms represented by R ²³ to R ²⁶ in the general formula (III) has 1 to 20 carbon atoms represented by R ¹ to R ³ in the general formula (I) It is similar to 20 hydrocarbon groups. Further, in the general formula (III) having 1 to 20 carbon atoms represented by ^{X 2} in Examples of the hydrocarbon group, the general formula of ^R 1 ~ 1 to 20 carbon atoms represented by ^{R 3} in (I) The bivalent group which removed one hydrogen atom from each group mentioned as a hydrocarbon group is mentioned.
The alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the arylalkyl group having 7 to 20 carbon atoms represented by R ²¹ and R ²² in the general formula (III) are respectively The alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, which is an example of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ³ , and the above 7 carbon atoms The same as described above for the -20 arylalkyl group.

The heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R ²¹ to R ²⁶ in the general formula (III) is a heterocyclic ring-containing carbon atom represented by R ¹ and R ² The same applies to the groups of 2 to 20.

Examples of the oxime ester compound (A2) include the compound No. 1 shown below. A2-1 to No. A2-14 can be mentioned. However, the oxime ester compound (A2) used in the present invention is not limited at all by the following compounds.

Other radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenyl phosphine oxide and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pill-1) -Yl)] Titanocene compounds such as titanium etc. may be mentioned.

Commercially available radical initiators include Adeka Optomer N-1414, N-1717, N-1919, Adeka Arkles NCI-831, NCI-930 (all manufactured by ADEKA Corporation); IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE 784 (above, made by BASF Corporation); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (above, made by TRONLY); Be

The thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and conventionally known compounds can be used. For example, azo compounds, peroxides and persulfates are preferable. It can be illustrated as a thing.

Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'- And azobis (1-acetoxy-1-phenylethane) and the like.

Examples of peroxides include benzoyl peroxide, di-t-butyl benzoyl peroxide, t-butyl peroxypivalate and di (4-t-butylcyclohexyl) peroxy dicarbonate.

Persulfates include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.

As the above-mentioned polymerization initiator (A) other than the component (A1), a polymerization initiator having a hydroxyl group is particularly preferable because it can provide a display having low liquid crystal contamination and excellent electrical characteristics.

In the case where X ¹ is a sulfur atom and X ² is non-bonding in the general formula (III), for example, compound No. 1 described above may be used. It is an oxime ester compound having a diphenyl sulfide skeleton represented by A2-1 to A2-7, and is preferably used in combination as a polymerization initiator from the viewpoint that a polymerizable composition having good sensitivity can be obtained.

In the case where X ¹ is NR ⁵⁵ and X ² is a direct bond in the general formula (III), for example, the compound No. 1 mentioned above may be used. It is an oxime ester compound having a carbazole skeleton represented by A2-8 to A2-14, which is particularly preferable in that a polymerizable composition having good sensitivity can be obtained.

The said polymerization initiator (A) can be mixed and used 1 type, or 2 or more types illustrated until now.

In the polymerizable composition of the present invention, the content of the polymerization initiator (A) is not particularly limited, but the polymerization initiator (A), the colorant (B), the alkali developable compound (C) And preferably 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, and more preferably 0 based on 100 parts by mass of a total of 100 parts by mass of the ethylenically unsaturated compound (D). 3 to 5 parts by mass. When the content of the polymerization initiator (A) is in the above range, a polymerizable composition having excellent curability and excellent storage stability without precipitation of the polymerization initiator can be obtained, which is preferable.
For example, in the case of forming a cured film having a thickness of 2 to 5 μm, the content of the polymerization initiator (A) is not particularly limited, but the polymerization initiator (A), the colorant (B), the alkali The amount is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, more preferably 0. It is 3 to 5 parts by mass.
Further, in view of elastic recovery, dielectric constant, electrical properties, etc., the proportion of the component (A1) in the polymerization initiator (A) is preferably 30% by mass or more, and more preferably 50% by mass to 85% by mass. When the component (A1) and the compound having a group represented by formula (I) are used in combination, the mass ratio of the component (A1) to the compound having a group represented by formula (I) (the former : The latter is preferably 2 to 5: 1, more preferably 2 to 3: 1.

<Colorant (B)>
As the colorant (B) used in the polymerizable composition of the present invention, pigments and dyes can be used. As the pigment and the dye, an inorganic color material or an organic color material can be used, respectively. These can be used alone or in combination of two or more. Here, the pigment means a coloring agent insoluble in a solvent described later, and among inorganic or organic coloring materials, those insoluble in a solvent, and those obtained by laked inorganic or organic dyes are also included.

Examples of the pigment include carbon black obtained by the furnace method, channel method or thermal method, carbon black such as acetylene black, ketjen black or lamp black, carbon black prepared or coated with epoxy resin, the above carbon black Prepared by dispersing the resin in a solvent in advance and coating with 20 to 200 mg / g of resin, acid or alkaline surface treatment of the carbon black, average particle diameter of 8 nm or more and DBP oil absorption of 90 ml / 100 g or less of carbon black, the total amount of oxygen calculated from CO and CO ₂ in the volatile content at 950 ° C. is, carbon black is surface area 100 m ² per 9mg above, graphitized carbon black, graphite, activated carbon, carbon fibers, carbon nanotubes, Kabonma Black pigments represented by crocoyl, carbon nanohorn, carbon aerogel, fullerene, aniline black, pigment black 7, titanium black, lactam black and perylene black etc., chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese based, ferrocyan , Phosphate blue, bitumen, ultramarine, cerulian blue, pyridinium, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, synthetic iron black, amber, lake pigment And organic or inorganic pigments such as

Among the above pigments, it is preferable to use a black pigment because of high light shielding property, and it is more preferable to use an organic black pigment represented by lactam black and perylene black because of low liquid crystal contamination.

A commercial item can also be used as said pigment, For example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97 , 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223 , 224, 226, 227, 254, 228, 240 and 254; pigment orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64 65 and 71; pigment yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 5, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180 and 185; pigment green 7, 10, 36 and 58; pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62 and 64; pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40 and 50 and the like.

Examples of the dye include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthantrone Examples thereof include compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids, azo dyes, metal complex compounds of cyanine dyes, and the like.

In the polymerizable composition of the present invention, the content of the colorant (B) is not particularly limited, but preferably 10 to 500 parts by weight with respect to 100 parts by weight of the following alkali developable compound (C). The amount is preferably 10 to 300 parts by mass, more preferably 10 to 200 parts by mass. When the content of the colorant (B) is within the above range, the polymerizable composition becomes excellent in storage stability without aggregation of the colorant, and the light shielding property of the cured product of the polymerizable composition is high. It is preferable because it becomes.
For example, in the case of forming a cured product with a thickness of 1 to 3 μm, the content of the colorant (B) is not particularly limited, but is preferably based on 100 parts by mass of the alkali developable compound (C). Is 10 to 500 parts by mass, more preferably 10 to 300 parts by mass, and still more preferably 10 to 200 parts by mass.

<Alkali developable compound (C)>
The alkali developable compound (C) according to the present invention is a compound having a hydrophilic group and exhibiting alkali developability. In the present invention, conventionally used compounds can be used as the alkali-developable compound (C) as long as the above conditions are satisfied.
Examples of the hydrophilic group include a hydroxyl group, a thiol group, a carboxyl group, a sulfo group, an amino group, an amido group or a salt thereof, and the hydroxyl group and the carboxyl group are the developability of the alkali developable compound (C) to an alkali. Is preferable because it is high.
The preferred functional group equivalent of the hydrophilic group in the alkali developable compound (C) (the mass of the polymer compound containing one equivalent of the hydrophilic group) is 50 to 10,000.
The weight average molecular weight of the alkali developable compound (C) is preferably 2,000 to 10,000, and particularly preferably 3,000 to 6,000. In addition, the number average molecular weight is from 1000 to 8000, in particular from 2000 to 5000. When the molecular weight of the alkali developable compound (C) is in the above range, a cured product which is excellent in developability and excellent in chemical resistance is preferably obtained.

The alkali developable compound (C) preferably has an acid value of 10 to 200 mg / KOH, more preferably 30 to 150 mg / KOH. If the acid value is less than 10 mg / KOH, the alkali developability may not be sufficiently obtained, and if it is more than 200 mg / KOH, production of the polymer compound may be difficult. Here, the acid value is in accordance with JIS K 0050 and JIS K 0211.

Specifically, as the alkali developable compound (C), a compound represented by the above general formula (II), a copolymer of acrylic acid ester, a phenol and / or cresol novolac epoxy resin, and a polyfunctional epoxy group Polyphenylmethane type epoxy resin; epoxy acrylate resin; epoxy addition compound having a structure in which unsaturated monobasic acid is added to an epoxy compound etc. represented by the following general formula (IV); It is represented by the following general formula (IV) A resin (unsaturated compound) having a structure obtained by the esterification reaction of an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound and a polybasic acid anhydride can be used.

(Wherein, M ⁴ is a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -O-, -S-, -SO _2- , -SS-, -SO-, -CO-, -OCO- or Represents a substituent selected from the group represented by the following formulas (a), (b), (c) or (d),
The hydrogen atom in the C1-C20 hydrocarbon group represented by M ⁴ may be substituted by a halogen atom, and R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ (hereinafter also described as R ³¹ to R ³⁸ ) each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, and k is a number of 0 to 10, , K ≧ 1, the plurality of R ³¹ to R ³⁸ and M ⁴ may be identical to or different from each other. )

(Wherein, R ³⁹ represents a hydrocarbon group having 1 to 20 carbon atoms,
R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ and R ⁶⁸ (hereinafter also referred to as R ⁴⁰ to R ⁶⁸ ) are each Independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocycle, or a halogen atom,
The methylene group in the group represented by R ³¹ to R ³⁸ and R ⁴⁰ to R ⁶⁸ may be substituted by an unsaturated bond, -O- or -S-.
R ⁴⁰ and R ⁴¹ , R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , R ⁴⁶ and R ⁴⁷ , R ⁴⁷ and R ⁴⁸ , R ⁵³ and R ⁵⁴ , R ⁵⁴ And R ⁵⁵ , R ⁵⁵ and R ⁵⁶ , R ⁶¹ and R ⁶² , R ⁶² and R ⁶³ , R ⁶³ and R ⁶⁴ , R ⁶⁵ and R ⁶⁶ , R ⁶⁶ and R ⁶⁷
And R ⁶⁷ and R ⁶⁸ may combine to form a ring,
In the groups represented by (a), (b), (c) and (d), * represents a bond. )

By using the alkali developable compound represented by the above general formula (II), a cured product obtained from the polymerizable composition is preferable because it is excellent in chemical resistance.

An epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the above general formula (IV); or an unsaturated monobasic acid to an epoxy compound represented by the above general formula (IV) The use of an alkali developable compound which is a reaction product obtained by the esterification reaction of an epoxy adduct compound having an adduct structure with a polybasic acid anhydride increases the sensitivity of the polymerizable composition, and the polymerizability is raised. A cured product obtained from the composition is preferred because of its excellent elastic recovery.

An epoxy compound in which the alkali developable compound (C) is represented by the above general formula (IV), because the dispersibility of the coloring agent (B) is good and the heat resistance is good; Epoxy compound having the following structure [(e)] in which unsaturated monobasic acid is added to the epoxy compound represented by IV); or by esterification reaction of such unsaturated compound and polybasic acid anhydride It is desirable that it is the unsaturated compound which has the following structure [(f)] obtained.

(Wherein, Y ⁷ represents a residue of unsaturated monobasic acid, Y ⁸ represents a residue of polybasic acid anhydride,
* Means a bond. )

In the alkali developable compound represented by the above general formula (IV), when M ⁴ is a group represented by (b) or (c), the solvent resistance of the cured product obtained from the polymerizable composition is It is particularly preferable because it becomes good.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ¹² , R ¹⁴ , R ¹⁶ , Y ¹ to Y ³ and Z ¹ to Z ³ in the above general formula (II) has the general formula (I) The same ones as the above-mentioned hydrocarbon group having 1 to 20 carbon atoms can be mentioned.

Groups having 2 to 20 carbon atoms containing the heterocycles represented by R ¹² , R ¹⁴ , R ¹⁶ , Y ¹ to Y ³ and Z ¹ to Z ³ in the above general formula (II), R ¹² , R The hydrogen atom in the group represented by ¹⁴ , R ¹⁶ , Y ¹ , Y ² , Y ³ , Z ¹ , Z ² and Z ³ may be substituted, and has 2 to 20 carbon atoms containing a heterocycle The same groups as the groups having 2 to 20 carbon atoms containing the heterocyclic ring described above in the description of the general formula (I) can be mentioned as the group of the above.

The hydrocarbon group having 1 to 20 carbon atoms represented by M ⁴ and R ³¹ to R ⁶⁸ in the general formula (IV) is a carbon having 1 to 20 carbon atoms as described in the description of the general formula (I) The same thing as a hydrogen group is mentioned.

As the group having 2 to 20 carbon atoms containing a heterocycle represented by R ⁴⁰ to R ⁶⁸ in the above general formula (IV), a carbon atom containing the heterocycle described above in the description of the general formula (I) The same groups as those of the formulas 2 to 20 can be mentioned.

The halogen atom for substituting the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms represented by M ⁴ in the general formula (IV) and the halogen atom represented by R ³¹ to R ⁶⁸ include fluorine and chlorine , Bromine and iodine.

R ⁴⁰ and R ⁴¹ , R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , R ⁴⁶ and R ⁴⁷ , R ⁴⁷ and R ⁴⁸ in the above general formula (IV) R ⁵³ and R ⁵⁴ , R ⁵⁴ and R ⁵⁵ , R ⁵⁵ and R ⁵⁶ , R ⁶¹ and R ⁶² , R ⁶² and R ⁶³ , R ⁶³ and R ⁶⁴ , R ⁶⁵ and R ⁶⁶ , R ⁶⁶ and R ⁶⁷ and R ⁶⁷ Examples of the ring formed by combining R ⁶⁸ and R ⁶⁸ include 5- to 7-membered rings such as cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, lactone ring and lactam ring And fused rings such as naphthalene and anthracene.

The unsaturated monobasic acid means an acid having an unsaturated bond in the structure and having one hydrogen atom per molecule which can be ionized to be a hydrogen ion.
Examples of the unsaturated monobasic acids include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid and hydroxyethyl methacrylate malate, hydroxypropyl methacrylate malate, hydroxypropyl acrylate malate and dicyclopentadiene malate, etc. Can be mentioned.

Moreover, as said polybasic acid anhydride made to act after making said unsaturated monobasic acid act, biphenyl tetracarboxylic acid dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, Trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic acid anhydride, ethylene glycol bisanhydrotrimellitate, glycerol trisanehydrotrimellitate, hexahydrophthalic anhydride Methyltetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene -1,2-dicarboxylic anhydride, trialkylte Rahidoro phthalic anhydride - maleic acid adduct, dodecenyl succinic anhydride, and anhydride and methyl high Mick acid.

It is preferable that the reaction molar ratio of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride be as follows.
That is, it is preferable to add the above-mentioned epoxy addition compound so that the carboxyl group of the above-mentioned unsaturated monobasic acid is in a ratio of 0.1 to 1.0 per one epoxy group of the above-mentioned epoxy compound. It is preferable that the reaction product be in a ratio such that the acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0 per hydroxyl group of the epoxy adduct.
The reaction of the epoxy compound represented by the above general formula (IV), the above unsaturated monobasic acid and the above polybasic acid anhydride can be carried out according to a conventional method.

In order to adjust the acid value and improve the developability of the polymerizable composition of the present invention, the photosensitive composition for BM and the photosensitive composition for BCS, a monofunctional or polyfunctional compound is further added together with the above alkali developable compound (C). Epoxy compounds can be reacted. The acid value of the solid content of the above alkali developable compound (C) is preferably in the range of 5 to 120 mg KOH / g, and the amount of the monofunctional or polyfunctional epoxy compound used is selected so as to satisfy the above acid value. Is preferred.

As the monofunctional epoxy compound, glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidyl agent , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl Glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monoxide, 1,2-epoxy-4- Vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, following epoxidation Things No. E1, No. E2 etc. are mentioned.

It is preferable to use one or more compounds selected from the group consisting of bisphenol type epoxy compounds and glycidyl ethers as the above-mentioned polyfunctional epoxy compound, because a polymerizable composition having better properties can be obtained.
As the above-mentioned bisphenol type epoxy compound, in addition to the epoxy compound represented by the above general formula (IV), for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used.
Further, as the above glycidyl ethers, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl Ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-to (Glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) can be used such as methane.
In addition, novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds, etc .; Alicyclic epoxy such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compounds; Glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester; tetraglycidyl diamino acid Glycidyl amines such as phenylmethane, triglycidyl P-aminophenol, N, N-diglycidyl aniline, etc .; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5, 5-dimethyl hydantoin, triglycidyl isocyanurate; Dioxide compounds such as pentadiene dioxide; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; dicyclopentadiene type epoxy compounds etc. can also be used.

A commercial item can also be used suitably as an alkali developable compound (C).
Examples of the commercially available product include SPC1000, SPC-2000, SPC-3000, SPRR-1X, SPRR-2X, SPRR-3X, SPRR-5X, SPRR-6X, SPRR-7X, SPRR-8X, SPRR-9X, and the like. SPRR-10X, SPRR-11X, SPRR-12X, SPRR-13X, SPRR-14X, SPRR-15X, SPRR-16X, SPRR-17X, SPRR-18X, SPRR-19X, SPRR-20X, SPRR-21X Showa Denko KK, JET 2000, AGOR 1060, AGOR 3060, ORGA 1060, ORGA 2060 (above, Osaka Organic Chemical Company), CCR-1171H (Nippon Kayaku Co., Ltd.), and the like.

In the polymerizable composition of the present invention, the content of the alkali developable compound (C) is not particularly limited, but the polymerization initiator (A), the colorant (B), the alkali developable compound (C) And preferably from 10 to 90 parts by mass, more preferably from 20 to 80 parts by mass, still more preferably from 30 to 80 parts by mass, based on 100 parts by mass of the total of the above and the ethylenically unsaturated compound (D). . When content of an alkali developable compound (C) is in said range, it is preferable from the alkali developability of a polymeric composition being favorable.
For example, in the case of forming a cured film having a thickness of 2 to 5 μm, the content of the alkali developable compound (C) is not particularly limited, but the polymerization initiator (A), the colorant (B), The amount is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, still more preferably, 100 parts by mass in total of the alkali developable compound (C) and the ethylenically unsaturated compound (D). 30 to 80 parts by mass.
When the alkali developable compound (C) contains a compound represented by the general formula (II), the amount thereof is as follows: polymerization initiator (A), colorant (B), alkali developable compound (C) and The amount is preferably 10 to 60 parts by mass, more preferably 20 to 50 parts by mass, based on 100 parts by mass of the ethylenically unsaturated compound (D) in total. Further, it is obtained by an esterification reaction of an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the above general formula (IV), or the epoxy addition compound and a polybasic acid anhydride. When the reaction product is contained, the amount thereof is 100 parts by mass in total based on the polymerization initiator (A), the colorant (B), the alkali developable compound (C) and the ethylenically unsaturated compound (D). Preferably, it is 5 to 80 parts by mass, more preferably 5 to 40 parts by mass. The above-mentioned epoxy addition compound and the content of the reaction product obtained by the esterification reaction of the epoxy addition compound with the polybasic acid anhydride refer to the case where only one of the epoxy addition compound and the reaction product is contained. If it contains both, it is the total amount.

<Ethylenically unsaturated compound (D)>
The ethylenically unsaturated compound (D) used in the present invention is a compound having an ethylenically unsaturated bond and which is not the above-mentioned alkali developable compound (C). Examples of the ethylenically unsaturated compound (D) include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid, α -Chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloylate Mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, such as hydroxyethyl, phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate; Ethyl (meth) acrylate malate, hydroxide Unsaturated polybasic acids such as cyclopropyl (meth) acrylate malate, dicyclopentadiene malate or polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups; (meth) acrylic Acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid glycidyl, the following acrylic compound No. 1 1 to No. 4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate ( (Meth) acrylate isooctyl, (meth) acrylate isononyl, (meth) acrylate stearyl, (meth) acrylate lauryl, (meth) acrylate methoxyethyl, (meth) acrylate dimethylaminomethyl, (meth) acrylate dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meth ) Ethyl hexyl acrylate, (meth) acrylic acid Noxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethane tri ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol ester Unsaturated monobasic acids such as la (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomers, etc. Polyhydric alcohol or ester of polyhydric phenol; Metal salt of unsaturated polybasic acid such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrofuran Phthalic anhydride-Male anhydride Acid anhydride, acid anhydride of unsaturated polybasic acid such as dodecenyl succinic anhydride, methyl hymic acid anhydride; (meth) acrylamide, methylene bis (meth) acrylamide, diethylene triamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyhydric amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanation Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinyl Unsaturated aromatic compounds such as phenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allylamine, N-vinyl pyrrolidone, vinyl piperidine Unsaturated amine compounds such as vinyl alcohol such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; maleimide, N-phenyl maleimide, N- Unsaturated imides such as cyclohexyl maleimide; Indens such as indene and 1-methyl indene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane; vinyl chloride, vinylidene chloride, divinyl succinyl And diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compounds of hydroxyl group-containing vinyl monomers and polyisocyanate compounds, hydroxyl group-containing Mention may be made of vinyl epoxy compounds of vinyl monomers and polyepoxy compounds.
The said ethylenically unsaturated compound (D) can be used individually or in mixture of 2 or more types.

A commercial item can also be used as said ethylenically unsaturated compound. Examples of the commercially available product include Kayalad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, R-684 (manufactured by Nippon Kayaku Co., Ltd.); Alonix M-215, M-350. NK ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N (all available from Shin-Nakamura Chemical Co., Ltd.); NK oligo U-4HA, U-4H, U-6HA, U-15HA, U-108A, U-1084A, U-200AX, U-122A, U-1000, SPC-3000 (all manufactured by Showa Denko KK); -340A, U-324A, UA-53H, UA-100, AH-600 (all available from Shin-Nakamura Chemical Co., Ltd.), UA-306H, AI-600, UA 101T, UA-101I, UA-306T, UA-306I (above, Kyoeisha Chemical Co., Ltd.), Art resin UN-9200A, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, SH-380G, SH- 500, SH-9832, UN-901T, UN-904, UN-905, UN-906, UN-906S, UN-952, UN-953, UN-953, UN-954, H-91, H-135 ( As described above, Netogami Kogyo Co., Ltd.), Sartomer CN 968, CN 975, CN 989, CN 9001, CN 9010, CN 9025, CN 9029, CN 9165, CN 2260 (all manufactured by Sartmar Corporation), EBECRYL 8810 (manufactured by Daicel Corporation), etc. may be mentioned.

In the polymerizable composition of the present invention, the content of the ethylenically unsaturated compound (D) is not particularly limited, but the polymerization initiator (A), the colorant (B), the alkali developable compound (C) 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 5 to 20 parts by mass, based on 100 parts by mass of the total of the ethylenic unsaturated compounds (D) is there. When content of an ethylenically unsaturated compound (D) is in said range, since the hardened | cured material obtained is excellent in curability and light-shielding property, it is preferable.
For example, in the case of forming a cured film having a thickness of 1 to 3 μm, the content of the ethylenically unsaturated compound (D) is not particularly limited, but the polymerization initiator (A), the colorant (B) The ethylenically unsaturated compound (D) is preferably 1 to 50 parts by mass, more preferably 1 to 50 parts by mass with respect to a total of 100 parts by mass of the alkali developable compound (C) and the ethylenically unsaturated compound (D). The amount is 30 parts by mass, more preferably 5 to 20 parts by mass.

A solvent can be further added to the polymerizable composition of the present invention. As the solvent, usually, the above-mentioned respective components (polymerization initiator (A), coloring agent (B), alkali developable compound (C) and ethylenic unsaturated compound (D), etc.) are dissolved or optionally, if necessary. Dispersible solvents can be used. For example, ketone solvents such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2- Ether solvents such as diethoxyethane and dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, 3-methoxybutyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and the like Ester solvents such as texanol; cellosolv solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso- or n- ester Alcohol solvents such as methanol, iso- or n-butanol and amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether (PGM), propylene glycol-1-monomethyl ether-2-acetate Ether ester solvents such as (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene; fats such as hexane, heptane, octane and cyclohexane Group hydrocarbon solvents; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirit, swasol # 310 (more, Cosmo Matsuyama Paraffin solvents such as Oil Co., Ltd .; and Solvesso # 100 (all, Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane Halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone And dimethylsulfoxide, water and the like, and these solvents can be used as one or more mixed solvents.

Among them, ketone solvents, ester solvents, ether ester solvents, etc., in particular cyclohexanone, 3-methoxybutyl acetate, dimethyl succinate and PGMEA etc., have good compatibility between the resist and the polymerization initiator in the polymerizable composition. preferable.

A combination of PGMEA, 3-methoxybutyl acetate and dimethyl succinate is preferable because a uniform coated surface can be obtained, so that the weight ratio of the above solvent (PGMEA: 3-methoxybutyl acetate: dimethyl succinate) is 15 to 25. The case of 2 to 5: 1 is particularly preferred.

In the polymerizable composition of the present invention, the content of the solvent is not particularly limited, but it is preferably 30 to 95% by mass in 100% by mass of the total amount of the polymerizable composition, more preferably 50 It is ̃95 mass%.
When the content of the solvent is in the above range, the handling property (viscosity and wettability of the polymerizable composition), unevenness of drying reduction and liquid stability (without precipitation and sedimentation of components contained in the composition) It is preferable because it becomes an excellent polymerizable composition, and the thickness of the cured product can be appropriately controlled when obtaining the cured product.

In the polymerizable composition of the present invention, if necessary, an epoxy compound, an alkali developability imparting agent, a dispersant, a latent additive, an organic polymer, an inorganic compound, a coupling agent, a chain transfer agent, and a sensitization. Polymerization inhibitors such as surfactants, surfactants and melamine compounds, p-anisole, hydroquinone, pyrocatechol, t-butyl catechol and phenothiazine; plasticizers; adhesion promoters; fillers; antifoams; leveling agents; Antioxidants; UV absorbers; dispersing aids; flocculants; catalysts; effect accelerators; crosslinking agents; conventional additives such as thickeners may be added.

Examples of the above epoxy compounds include methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, C12 to 13 mixed alkyl glycidyl ether, phenyl 2-methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, Glycidyl methacrylate, isopropyl glycidyl ether, allyl glycidyl ether, ethyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 4-n-butylphenyl glycidyl ether, 4-phenylphenol glycidyl ether, cresyl glycidyl ether, dibromocresyl Glycidyl ether, decyl glycidyl ether, methoxypolyethylene glycol Cole monoglycidyl ether, ethoxy polyethylene glycol monoglycidyl ether, butoxy polyethylene glycol monoglycidyl ether, phenoxy polyethylene glycol monoglycidyl ether, dibromophenyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether Glycidyl ether compounds such as 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,1,2,2-tetrakis (glycidyloxyphenyl) ethane and pentaerythritol tetraglycidyl ether; glycidyl acetate, glycidyl stear Glycidyl esters such as acrylate; 2- (3,4-epoxycyclohexyl-5,5-spi -3,4-Epoxy) cyclohexane-metadioxane, methylene bis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4-) Epoxycyclohexyl) propane, ethylenebis (3,4-epoxycyclohexanecarboxylate), bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyl Epoxy-1-methylcyclohexyl 3,4-epoxy-1-methylhexane carboxylate, 6-methyl-3,4-epoxycyclohexylmethyl 6-methyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-3 -Methyl Chlorohexylmethyl 3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl 3,4-epoxy-5-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxy Epoxy cyclos such as cyclohexane, 1,2-epoxy-2-epoxyethyl cyclohexane, dicyclopentadiene diepoxide, 3,4-epoxy-6-methylcyclohexyl carboxylate, α-pinene oxide, styrene oxide, cyclohexene oxide and cyclopentene oxide Alkyl type compounds and N-glycidyl phthalimide etc. may be mentioned.

An epoxidized polyolefin can also be used as said epoxy compound. The epoxidized polyolefin is a polyolefin in which an epoxy group is introduced by modifying the polyolefin with an epoxy group-containing monomer. Producing by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and, if necessary, another monomer by either a copolymerization method or a graft method it can. Ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer and another monomer may be polymerized alone or in combination with other monomers. Also, the double bond of a non-conjugated polybutadiene having a hydroxyl group at the end can be obtained by epoxidation by the peracetic acid method, and one having a hydroxyl group in the molecule may be used. Moreover, a hydroxyl group can be urethane-ized with isocyanate, and a primary hydroxyl group-containing epoxy compound can be made to react here, and an epoxy group can be introduce | transduced.

Examples of ethylene or α-olefins of 3 to 20 carbon atoms include ethylene, propylene, butylene, isobutylene, 1,3-butadiene, 1,4-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3 -Butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and the like can be mentioned.

Examples of the epoxy group-containing monomer include glycidyl esters of α, β-unsaturated acids, vinyl benzyl glycidyl ether and allyl glycidyl ether. Specific examples of glycidyl esters of α, β-unsaturated acids include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylic acid, with glycidyl methacrylate being particularly preferred.

A commercial item can also be used as said epoxy compound. Suitable commercial products include, for example, Epolight 40E, 1500 NP, 1600, 80 MF, 4000 and 3002 (all, manufactured by Kyoeisha Chemical Co., Ltd.); Adeka Glycyrol ED-503, ED-503 D, ED-503 G, ED-523 T, ED -513, ED-501, ED-502, ED-509, ED-518, ED-529, Adeka Resin EP-4000, EP-4005, EP-4080 and EP-4085 (all from Adeka); Denacol EX- 201, EX-203, EX-211, EX-212, EX-221, EX-251, EX-252, EX-711, EX-721, Denacol EX-111, EX-121, EX-141, EX-142 , EX-145, EX-146, EX-147, EX-171, EX-192 and EX-731 (above, Nagase ChemteX Corporation); EHPE-3150, Celoxides 2021 P, 2081, 2000 and 3000 (above, Daicel Corporation); Epiol M, EH, L-41, SK, SB, TB and OH ( Above, manufactured by NOF Corporation; Epolight M-1230 and 100 MF (all, manufactured by Kyoeisha Chemical Co., Ltd.); Aron oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211 and OXT-212 Etanacol OXBP and OXTP (above, Ube Industries, Ltd.); 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether and 4-hydroxybutyl vinyl ether (above, Maruzen Petrochemical Co., Ltd.); 121, EX-141, EX- 42, EX-145, EX-146, EX-147, EX-201, EX-203, EX-711, EX-721, On Coat EX-1020, EX-1030, EX-1040, EX-1050, EX- 1051, EX-1010, EX-1011 and 1012 (all manufactured by Nagase ChemteX Corp.); Ogsol PG-100, EG-200, EG-210 and EG-250 (all manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D And HP 4700 (all manufactured by DIC); ESN-475V (manufactured by Tohto Kasei Co., Ltd.); Marproof G-0105SA and G-0130SP (all manufactured by NOF Corporation); Epiclon N-665 and HP-7200 (all manufactured by DIC) EOCN-1020, EOCN-102S, EOCN-103S, EOCN 104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H and NC-7000L (manufactured by Nippon Kayaku Co., Ltd.).

The above-mentioned alkali developing property imparting agent is a compound which does not have radical polymerizability and imparts alkali developing property, and as such a compound, it is a compound which is soluble in an aqueous alkali solution by having an acid value. Although not particularly limited, alkali-soluble novolak resins (hereinafter simply referred to as "novolak resins") are mentioned as typical ones. Novolak resins are obtained by polycondensation of phenols and aldehydes in the presence of an acid catalyst.

Examples of the above-mentioned phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2- Methyl resorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester and the like are used. Among these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5- Shirenoru, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methyl resorcinol and bisphenol A are preferable. These phenols may be used alone or in combination of two or more.

Examples of the aldehyde include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o -Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methyl benzaldehyde, m-methyl benzaldehyde, p-methyl benzaldehyde, p-ethyl benzaldehyde and p -N-butyl benzaldehyde etc. are used, and of these compounds Aldehyde, acetaldehyde and benzaldehyde are preferred. These aldehydes may be used alone or in combination of two or more. The aldehydes are preferably used in a proportion of 0.7 to 3 moles, particularly preferably 0.7 to 2 moles, per mole of phenols.

As the acid catalyst, for example, an inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid, or an organic acid such as formic acid, oxalic acid or acetic acid is used. The amount of these acid catalysts used is preferably 1 × 10 ^-4 to 5 × 10 ^-1 mol per mole of phenol. In the condensation reaction, water is usually used as the reaction medium, but when the phenols used in the condensation reaction do not dissolve in the aqueous solution of aldehydes and become heterogeneous from the initial stage of the reaction, they are hydrophilic as the reaction medium Solvents can also be used. These hydrophilic solvents include, for example, alcohols such as methanol, ethanol, propanol and butanol, or cyclic ethers such as tetrahydrofuran and dioxane. The amount of the reaction medium used is usually 20 to 1000 parts by mass per 100 parts by mass of the reaction raw material. The reaction temperature of the condensation reaction can be appropriately adjusted depending on the reactivity of the reaction raw material, but it is usually 10 to 200 ° C., preferably 70 to 150 ° C. After completion of the condensation reaction, the internal temperature is generally raised to 130 to 230 ° C. in order to remove unreacted raw materials, acid catalyst and reaction medium present in the system, and volatile components are distilled off under reduced pressure, and then The molten novolak resin is collected by flowing on a steel belt or the like.
After completion of the condensation reaction, the reaction mixture is dissolved in the hydrophilic solvent and added to a precipitant such as water, n-hexane and n-heptane to precipitate the novolac resin, and the precipitate is separated and dried by heating. It can also be collected by

As examples other than the above novolak resin, polyhydroxystyrene or a derivative thereof, styrene-maleic anhydride copolymer, polyvinyl hydroxybenzoate and the like can be mentioned.

Any dispersant may be used as the dispersant, as long as it can disperse and stabilize the colorant (B), and commercially available dispersants such as BYK series manufactured by Bick Chemie Co., Ltd. can be used, and polyester having a basic functional group , A polymer dispersant comprising a polyether, a polyurethane, a nitrogen atom as a basic functional group, and a functional group having a nitrogen atom is an amine and / or a quaternary salt thereof, and has an amine value of 1 to 100 mg KOH / g Is preferably used.

The latent additive is inert at room temperature, in the light exposure step and the pre-bake step, and is heated at 100 to 250 ° C. or protected at 80 to 200 ° C. in the presence of an acid / base catalyst. Is to be desorbed and activated. As an effect obtained by having activated, oxidation prevention, ultraviolet-ray absorption, antifouling property, recoat property, adhesiveness, etc. are mentioned.
As the latent additive, those described in WO 2014/021023 can be preferably used.

A commercial item can be used as the latent additive, and examples thereof include Adeka Arkles GPA-5001 and the like.

Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene-(meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Polyester, phenol resin, phenoxy resin, polyamide imide resin, polyamic acid resin, epoxy resin, etc. may be mentioned. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, epoxy resin Masui.
The properties of the cured product can also be improved by using the organic polymer together with the alkali developable compound (C).
When an organic polymer is used, the amount thereof used is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the alkali developable compound (C).

Examples of the above-mentioned inorganic compounds include nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, metal oxides such as silica and alumina; layered clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenide, aluminum silicate, calcium silicate, aluminum silicate, aluminum hydroxide, platinum, gold, silver and copper Among these, titanium oxide, silica, layered clay minerals, silver and the like are preferable.

By incorporating an inorganic compound in the polymerizable composition of the present invention, it can be used as a photosensitive paste composition. The photosensitive paste composition is used to form fired product patterns such as partition patterns, dielectric patterns, electrode patterns and black matrix patterns of plasma display panels.
These inorganic compounds are also suitably used as, for example, fillers, antireflective agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.

In the polymerizable composition of the present invention, when an inorganic compound is added, the content of the inorganic compound is preferably 0.1 to 50 parts by mass, relative to 100 parts by mass of the alkali developable compound (C). The amount is preferably 0.5 to 20 parts by mass, and these inorganic compounds may be used alone or in combination of two or more.

Examples of the coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane and the like. Alkenyl functional alkoxysilanes such as alkyl functional alkoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, etc. Ta) Acrylic ester functional alkoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (3 Epoxy functional alkoxysilanes such as (4,4-epoxycyclohexyl) propyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyl Aminofunctional alkoxysilanes such as trimethoxysilane, mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, isocyanate functional alkoxysilanes such as 3-isocyanatopropyltriethoxysilane, 3-ureidopropyl Ureido functional alkoxysilanes such as alkoxysilanes, isocyanurate functional alkoxysilanes such as tris- (trimethoxysilylpropyl) isocyanurate, titanium alkoxides such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium dioctyloxy Titanium chelates such as bis (octylene glycolate), titanium diisopropoxy bis (ethyl acetoacetate), zirconium chelates such as zirconium tetraacetylacetonate, zirconium tributoxy monoacetylacetonate, zirconium tributoxy monostearate, etc. Zirconium acylates, and isocyanate silanes such as methyl triisocyanate silane can be used.
The addition of a coupling agent is preferable because it improves the adhesion between the cured product and the substrate (particularly glass).

A commercial item can be used as said coupling agent, For example, KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-403, KBM- 502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007, KBM-04, KBE-04, KBM-13, KBE-13, KBE-22, KBE-KBE 103, HMDS-3, KBM-3063, KBM-3103C, KP -3504 and KF-99 (or, Shin-Etsu Silicone Co., Ltd.).

A sulfur atom-containing compound is generally used as the chain transfer agent and the sensitizer. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-Mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol tetrakis (3- 3- Mercapto compounds such as mercapto propionate); Disulfide compounds obtained by oxidizing the mercapto compounds; iodoacetic acid, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid and iodomethane such as 3-iodopropanesulfonic acid Alkylated compounds; trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1, -Dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropio , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, tris hydroxyethyl tris thiopropionate, compound No. 1 below. C1, Karens PE-1 and NR1 manufactured by Showa Denko K. K.

It is preferable because the pattern of the cured product obtained by adding the above-mentioned chain transfer agent and sensitizer becomes high definition.

Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates, and higher amines Cationic surfactants such as halides and quaternary ammonium salts, polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, nonionic surfactants such as fatty acid monoglycerides, amphoteric surfactants and silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

Examples of the melamine compound, (poly) methylol melamine, (poly) methylol glycoluril, all or part of the (poly) methylol benzoguanamine and (poly) active methylol groups of the nitrogen compound such as methylol urea (CH 2 _OH groups) Mention may be made of compounds in which (at least two) are alkyletherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group and a butyl group, which may be identical to or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensing within one molecule, or may be condensed between two molecules to form an oligomer component as a result. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril and tetrabutoxymethylglycoluril can be used. Among these, alkyletherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.

In the polymerizable composition of the present invention, the content of optional components other than the polymerization initiator (A), the colorant (B), the alkali developing compound (C), the ethylenically unsaturated compound (D), the solvent and the inorganic compound Is appropriately selected depending on the purpose of use, and is not particularly limited as long as the effects of the present invention are not impaired, but preferably, polymerization initiator (A), colorant (B), alkali developable compound (C) The total amount is 20 parts by mass or less based on 100 parts by mass of the total of 100 parts by mass of the ethylenically unsaturated compound (D).

The photosensitive composition for BM according to the present invention contains, as essential components, a polymerization initiator (A), a colorant (B), an alkali developing compound (C) and an ethylenically unsaturated compound (D), and is photosensitive. And alkali developability, and is a composition particularly suitable for forming a BM.

The photosensitive composition for BCS of the present invention contains, as essential components, a polymerization initiator (A), a colorant (B), an alkali developable compound (C) and an ethylenically unsaturated compound (D), and is photosensitive. And alkali developability, and is a composition particularly suitable for forming BCS.

The polymerizable composition of the present invention, the photosensitive composition for BM or the photosensitive composition for BCS and the cured product are curable paint, varnish, curable adhesive, printed circuit board, display device (color TV, PC monitor, Color filters in color display liquid crystal display panels such as portable information terminals and digital cameras, color filters for various display applications, color filters for CCD image sensors, touch panels, electroluminescent display devices (partition materials for micro LEDs), plasma display Manufacturing process of panel, organic EL black partition, powder coating, printing ink, printing plate, adhesive, gel coat, photoresist for electronics, electroplating resist, etching resist, solder resist, insulating film, black matrix, and LCD Resists to form structures in Composition for Encapsulating Electronic Component, Solder Resist, Magnetic Recording Material, Micro Mechanical Component, Waveguide, Optical Switch, Plating Mask, Etching Mask, Color Test System, Glass Fiber Cable Coating, Stencil for Screen Printing, Stereolithograph Materials for producing three-dimensional objects, materials for holographic recording, image recording materials, microelectronic circuits, bleaching materials, bleaching materials for image recording materials, bleaching materials for image recording materials using microcapsules, Use in various applications such as photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, and photoresist materials and protective films used for dielectric layer formation in successive lamination of printed circuit boards There are no particular restrictions on its use, but there are The play display, out be particularly suitably used.

The display device of the present invention has the same structure as a conventionally known display device except that it comprises the cured product of the present invention (in particular, BCS), but BCS may be provided between cells.

When the polymerizable composition of the present invention is used as a black partition wall of an organic EL, an alkali developable compound having a weight average molecular weight of 5000 or more may be used because the pattern shape is verticalized, the development adhesion is improved, and the heat resistance is improved. It is preferable to use an alkali developable compound having a weight average molecular weight of 7000 to 15,000. Further, it is obtained by an esterification reaction between an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the above general formula (IV), and an polybasic acid anhydride. Particularly preferred is the unsaturated compound having the following structure.

The method for producing a cured product using the polymerizable composition of the invention, the photosensitive composition for BM and the photosensitive composition for BCS will be described in detail below.

The polymerizable composition of the present invention, the photosensitive composition for BM and the photosensitive composition for BCS can be prepared by a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, immersion and the like. It can be applied on a supporting substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic and the like. In addition, once applied on a supporting substrate such as a film, it can be transferred onto another supporting substrate, and the method of application is not limited.

Moreover, as a light source of energy rays used when curing the polymerizable composition of the present invention and the photosensitive composition for BCS, an ultra high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, mercury vapor Electromagnetic wave energy or electron beam having a wavelength of 2000 angstrom to 7000 angstrom obtained from arc lamp, xenon arc lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excimer lamp, germicidal lamp, light emitting diode, CRT light source etc. Although high energy rays such as X-rays and radiation can be used, preferably, ultra-high pressure mercury lamps that emit light with a wavelength of 300 to 450 nm, mercury vapor arc lamps, carbon arc lamps, xenon arc lamps and the like can be mentioned. .

Furthermore, by using a laser beam as an exposure light source, a laser direct writing method of directly forming an image from digital information of a computer or the like without using a mask improves not only productivity but also resolution and positional accuracy. It is useful because it can also be used, and light with a wavelength of 340 to 430 nm is suitably used as the laser light, but excimer lasers, nitrogen lasers, argon ion lasers, helium cadmium lasers, helium neon lasers, krypton ion lasers Also usable are those emitting light in the visible to infrared region such as various semiconductor lasers and YAG lasers. When using these lasers, sensitizing dyes that absorb the relevant region of visible to infrared are added.

The cured products of the present invention are particularly useful as BCS. (1) forming a coating film of the photosensitive composition for BCS of the present invention on a substrate, (2) irradiating the coating film with radiation through a mask having a predetermined pattern shape, 3) Baking step after exposure, (4) Step of developing the film after exposure, (5) Step of heating the film after development
As the mask, a multi-tone mask such as a halftone mask or a gray scale mask can also be used.

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to these examples and the like.

Preparation Example 1 Preparation of Lactam Black Dispersion B-1 Organic Black Pigment (Black 582 as Lactam; manufactured by BASF), Dispersant (BYK-167), Polymer for Dispersion (Alkali Development Described Below) Functional compound PGMEA solution C-2) in 16 parts by mass, 3.2 parts by mass and 3.6 parts by mass, respectively, to this mixture are added propylene glycol monomethyl ether acetate (PGMEA) at a solid concentration of 25 The mixture was weighed and added so as to be% by mass.
After the above mixture is premixed with a stirrer, 0.3 mm diameter zirconia beads are added in the same weight as the dispersion (the mixture minus the solvent PGMEA) and painted for 6 hours at a temperature of 25 to 60 ° C. After the dispersion was treated with a shaker, the zirconia beads were removed using a filter to obtain a dispersion. PGMEA was added to the obtained dispersion, and the dispersion concentration was adjusted to 20% by mass, and after making uniform with a stirrer, lactam black dispersion B-1 was obtained.

Preparation Example 2 Preparation of Perylene Black Dispersion B-2 Organic Black Pigment [C. I. Pigment black 31 (PalIogenBlackS0084; manufactured by BASF Corp.)], dispersant (BYK-167) and polymer for dispersion (alkaline developable compound PGMEA solution C-2 described later) each in 12 parts by mass, 3.6 parts After mixing in parts by mass and 8 parts by mass, propylene glycol monomethyl ether acetate (PGMEA) was weighed and added to this mixture so as to have a solid content concentration of 25% by mass to prepare a mixture.
After the above mixture is premixed with a stirrer, 0.3 mm diameter zirconia beads are added in the same weight as the dispersion (the mixture minus the solvent PGMEA) and painted for 6 hours at a temperature of 25 to 60 ° C. After the dispersion was treated with a shaker, the zirconia beads were removed using a filter to obtain a dispersion. PGMEA was added to the obtained dispersion, and the dispersion concentration was adjusted to 20% by mass, and after making uniform using a stirrer, a perylene black dispersion B-2 was obtained.

Preparation Example 3 Preparation of Carbon Black Dispersion B-3 20 parts by mass of MA100 (manufactured by Mitsubishi Chemical Corporation) as carbon black, and 12.5 parts by mass of BYK 161 (manufactured by BIC Chemie (BYK)) as a dispersing agent (solid content concentration 40 mass%) and 67.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed and treated by a bead mill to prepare carbon black dispersion liquid B-3.

Preparation Example 4 Preparation of Alkali Developing Compound PGMEA Solution C-2 184 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 58 g of acrylic acid, 2,6-di-tert 0.26 g of -butyl-p-cresol, 0.11 g of tetra-n-butylammonium bromide and 105 g of PGMEA were charged and stirred at 120 ° C. for 16 hours. The reaction solution was cooled to room temperature, 160 g of PGMEA, 59 g of biphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120 ° C. for 4 hours. Further, 20 g of tetrahydrophthalic anhydride is added, and the mixture is stirred at 120 ° C. for 4 hours, 100 ° C. for 3 hours, 80 ° C. for 4 hours, 60 ° C. for 6 hours, 40 ° C. for 11 hours. As a result, an alkali developable compound C-2 was obtained (Mw = 5000, Mn = 2100, acid value (solid content) 92.7 mg KOH / g). The content of the alkali developable compound in the alkali developable compound PGMEA solution C-2 was 45% by mass.

Preparation Example 5 Preparation of Alkali-Developable Compound PGMEA Solution C-3 75.0 g of 9,9-bis (4-glycidyloxyphenyl) fluorene, 23.8 g of acrylic acid, 2,6-di-t-butyl-p 0.273 g of cresol, 0.585 g of tetrabutylammonium chloride and 65.9 g of PGMEA are charged and stirred at 90 ° C. for 1 hour, 100 ° C. for 1 hour, 110 ° C. for 1 hour and 120 ° C. for 14 hours. The mixture was cooled to room temperature, 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride and 1.37 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Furthermore, 30.0 g of 9,9-bis (4-glycidyloxyphenyl) fluorene, 0.269 g of 2,6-di-t-butyl-p-cresol, and 1.50 g of PGMEA are added, and the mixture is heated at 90 ° C. for 90 minutes. After stirring for 4 hours at 120 ° C., 122.2 g of PGMEA was added to obtain an alkali developable compound C-3 as a target product as a PGMEA solution (Mw = 4190, Mn = 2170, acid value (solid content) 52 mg · KOH) / G). The content of the alkali developable compound in the alkali developable compound PGMEA solution C-3 was 45% by mass.

[Examples 1 to 14 and Comparative Examples 1 to 5] Preparation of Polymerizable Composition Each component is mixed according to the composition of [Table 1] to [Table 4], and polymerizable compositions (Examples 1 to 12 and Comparative Example) I got 1 to 5). In addition, the numerical value of the composition in a table represents a mass part.
Moreover, the code | symbol of each component in a table | surface represents the following components.
A1-1 Compound No. A1-1 [polymerization initiator belonging to component (A1)]
A2-1 Compound No. A2-1 [polymerization initiator belonging to (A2) component]
A2-2 Compound No. A2-8 [polymerization initiator belonging to (A2) component]
A2-3 Compound No. A2-14 [polymerization initiator belonging to (A2) component]
A3-1 IRGACURE 907
(Α-Aminoacetophenone compound having no hydroxyl group; manufactured by BASF)
B-1 Lactam black dispersion B-1
B-2 Perylene Black Dispersion B-2
B-3 Carbon Black Dispersion B-3
C-1 CCR-1171H
(Alkali Developing Compound PGMEA Solution Represented by General Formula (II) Solid Content 69.5% by Mass; Nippon Kayaku Co., Ltd. C-2 Alkaline Developing Compound PGMEA Solution C-2
C-3 Alkali developable compound PGMEA solution C-3
D-1 Kayarad DPHA (ethylenically unsaturated compound; manufactured by Nippon Kayaku Co., Ltd.)
D-2 UA-306H (urethane monomer, PETA + HDI)
E-1 γ-Glycidoxypropyltrimethoxysilane (Coupling Agent)
E-2 Karenz PE-1 (thiol compound; manufactured by Showa Denko)
G-1 PGMEA
G-2 3-methoxybutyl acetate G-3 dimethyl succinate

[Evaluation of Cured Product Obtained from Polymerizable Composition]
Evaluation of elastic recovery factor, light blocking property (OD value), relative dielectric constant, liquid crystal contamination (VHR) and chemical resistance of cured products obtained from the polymerizable compositions of Examples 1 to 14 and Comparative Examples 1 to 5. The following procedure was followed. The results are shown in [Table 1] to [Table 4].

(Elastic recovery rate)
The polymerizable compositions of Examples 1 to 14 and the comparative polymerizable compositions of Comparative Examples 1 to 5 are applied by spin coating (3 μm thickness, 300 rpm × 7 seconds) on a glass substrate and dried for 100 seconds at 90 ° C. After pre-baking and removing the solvent, after exposure with a photomask using a high pressure mercury lamp at 100 mJ / cm ² and development using a 0.04 mass% KOH aqueous solution, 30 at 230 ° C. Heated for a minute to create a pattern. A 20 μm portion of the obtained pattern was subjected to a load-unload test at 40 mN using a Shimadzu dynamic microhardness tester DUH-211. The elastic recovery rate (%) was calculated by the following formula.

Elastic recovery rate (%) = [(recovery distance / compression displacement) x 100]

A cured product having an elastic recovery rate (%) of 60% or more can be used as BCS, a cured product having an elastic recovery rate (%) of 70% or more can be preferably used as BCS, and an elastic recovery rate Cured products having (%) of 80% or more can be particularly preferably used as BCS.

(OD value)
The polymerizable compositions of Examples 1 to 14 and the comparative polymerizable compositions of Comparative Examples 1 to 5 were spin-coated (300 rpm, 7 seconds) and dried on a glass substrate, and then prebaked at 90 ° C. for 100 seconds. . After exposure using an ultra-high pressure mercury lamp as a light source, a cured product was formed by baking at 230 ° C. for 30 minutes. The OD value of the obtained film was measured using a Macbeth permeation densitometer, and the OD value was divided by the film thickness after post-baking to calculate the OD value per film thickness.
A cured product having an OD value per film thickness of 1.0 or more can be used as a BCS because the light shielding property is high, and a cured product having an OD value per film thickness of 1.5 or more is preferably used as a BCS A cured product having an OD value per film thickness of 2.0 or more can be particularly preferably used as BCS. A cured product having an OD value of less than 1.0 per film thickness can not be used as a BCS.

(Dielectric constant)
After spin coating (3 μm thickness, 300 rpm × 7 seconds) of the polymerizable compositions of Examples 1 to 14 and the comparative polymerizable compositions of Comparative Examples 1 to 5 on a glass substrate and drying, they are then subjected to 100 seconds at 90 ° C. After prebaking and exposing with a high pressure mercury lamp at 100 mJ / cm ² without using a mask, the sample was heated at 230 ° C. for 180 minutes to form the above evaluation sample. (Evaluation Method) The above-mentioned evaluation sample was measured by applying an AC of 1 V and 1 kHz using an LCR meter, Agilent 4284A.
A cured product having a dielectric constant of less than 5.0 can be used as BCS, a cured product having a dielectric constant of 4.5 or less can be preferably used as a BCS, and a cured product having a dielectric constant of 4.0 or less It can be particularly preferably used as BCS. A cured product having a relative dielectric constant of 5.0 or more can not be used as a BCS.

(VHR)
The polymerizable compositions obtained in Examples 1 to 14 and the comparative polymerizable compositions obtained in Comparative Examples 1 to 5 were coated on a glass substrate (100 mm × 100 mm) using a spin coater and at 90 ° C. Pre-baking was performed for 100 seconds to form a coating having a thickness of 3.0 μm. Then, using a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the coating film was irradiated with ultraviolet light at an irradiation amount of 200 mJ / cm ² without using a mask. Thereafter, post-baking was performed at 230 ° C. for 30 minutes.
One part by mass of the post-baked coating was mixed with 40 parts by mass of liquid crystal “RS-182” manufactured by ADEKA Corporation, and stored at 120 ° C. for 1 hour. This was taken out to room temperature and allowed to stand, and then the supernatant was collected. The VHR (voltage holding ratio) of the collected liquid crystal composition was measured. The detailed evaluation method is as follows. The liquid crystal composition was injected into a TN cell for liquid crystal evaluation (cell thickness 5 μm, electrode area 8 mm × 8 mm alignment film JALS 2096), and VHR was measured using VHR-1A (manufactured by Toyo Corporation). (Measurement conditions: Pulse voltage width 60 μs, frame period 16.7 ms, wave height ± 5 V, measurement temperature 60 ° C.)
Cured products with VHR of 90% or more are low in liquid crystal stain and can be used as BCS, and cured products with VHR of 95% or more can be preferably used as BCS, and VHR is 98 or less. % Or more of the cured product can be particularly preferably used as BCS.
Cured products with VHR less than 90% can not be used as BCS.

<NMP chemical resistance>
The N-methyl pyrrolidone (NMP) dissolution test was performed according to the following procedure.
First, the prepared polymerizable compositions obtained in Examples 1 to 14 and the comparative polymerizable compositions obtained in Comparative Examples 1 to 5 were treated with a spin coater to obtain a glass substrate with a final film thickness of 3 μm. And dried for 1 minute and then dried on a hot plate at 90.degree. C. for 120 seconds. After exposure with a high-pressure mercury lamp at 50 mJ / cm ² and development, the substrate was heated at an oven temperature of 230 ° C. for 40 minutes to obtain a resist coated substrate. Two substrates for measurement (25 mm × 35 mm square) were cut out from the produced resist-coated substrate and immersed in a 10 mL vial containing 8 mL of N-methylpyrrolidone (NMP). And the NMP elution test was implemented in the state which left the vial bottle containing the substrate for measurement in a clean oven of 90 degreeC for 60 minutes. After standing for 40 minutes, the vial was removed from the heat bath, and the NMP-eluted solution was measured for absorbance at 1 nm intervals in a wavelength range of 300 to 800 nm using a spectrophotometer (“UV-3100 PC” manufactured by Shimadzu Corporation). A halogen lamp and a deuterium lamp (switching wavelength: 360 nm) are used as a light source, and a photomar is used as a detector, and a slit width of 2 nm is used as a measurement condition. The sample solution is placed in a 1 cm square quartz cell and measured. Absorbance is a dimensionless quantity that indicates how much the light intensity attenuates when light passes through an object in spectroscopy, and is defined by the following equation.

A (absorbance) = -log ₁₀ (I / I ₀ ) (I: transmitted light intensity, I ₀ : incident light intensity)

Further, the incident light intensity and the transmitted light intensity described above are the light intensity I ₀ transmitted through NMP alone and the light intensity I transmitted through the sample solution when light is made incident respectively to the sample solution and NMP alone from the same light source It can be considered. Therefore, (I / I ₀ ) in the above equation represents the light transmittance, and the absorbance A is a value obtained by logarithmically expressing the reciprocal of the transmittance. The absorbance A is a notation used when calculating the concentration or the like of a substance contained in a sample solution. In the case of the absorbance A = 0, it shows a state of not absorbing light at all (transmission rate 100%), and in the case of the absorbance A = ∞, it shows a state of not transmitting light at all (transmission rate 0%). become. That is, the stronger the absorbance, the more the resist coating component dissolves into NMP, indicating that the NMP resistance is worse. The spectral area (nm) of the measured absorbance was calculated, and the evaluation was performed based on the following criteria.
NMP chemical resistance evaluation criteria: Determination by the area value of the absorption spectrum of NMP elution solution (wavelength 300 to 800 nm)
○: less than 20 (nm) Δ: 20 (nm) or more and 60 (nm) or less ×: 60 (nm) or more NMP chemical resistance evaluation is ○ that can be particularly preferably used as BCS, those that are Δ , Can be used as BCS, those of x can not be used as BCS.
The spectral area of the absorbance, which is the evaluation criterion, can be represented by the sum of absorbance at each wavelength, and means the sum of the eluted resist components.

As apparent from [Table 1] to [Table 4], the cured product obtained from the polymerizable composition of the present invention has a light shielding property (OD value), a relative dielectric constant, low liquid crystal contamination (VHR), and chemical resistance. It is useful as BCS because it has excellent elasticity recovery rate after satisfying the properties at a high level.

The cured product obtained from the polymerizable composition of the present invention, the photosensitive composition for BM or the photosensitive composition for BCS is excellent in elastic recovery, light shielding property, chemical resistance, low dielectric constant, and good electrical characteristics. It is a cured product, particularly suitable for BCS. The cured product is particularly useful for display devices and the like.

Claims

A polymerizable composition comprising a polymerization initiator (A), a colorant (B), an alkali developable compound (C) and an ethylenically unsaturated compound (D) excluding the alkali developable compound (C),
A polymerizable composition, wherein the polymerization initiator (A) contains an α-aminoacetophenone compound (A1) having a hydroxyl group.
The said polymerization initiator (A) is added to the alpha-amino acetophenone compound (A1) which has a hydroxyl group, and contains the oxime ester compound (A2) which has a group represented with the following general formula (I). Polymerizable composition.

(Wherein, R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocycle) Represents
The hydrogen atom in the group represented by R 1 and R 2 is a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, It may be substituted with an isocyanate group or a group having 2 to 20 carbon atoms containing a heterocycle, and the methylene group in the groups represented by R 1 and R 2 is —O—, —CO—, —COO— , -OCO -, - NR 3 - , - NR 3 CO -, - S -, - CS -, - SO 2 -, - SCO -, - COS -, - OCS-, substituted with an unsaturated bond or CSO- In some cases,
R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
m represents 0 or 1;
* In the formula represents a bond. )
The polymerizable composition according to claim 1 or 2, wherein the colorant (B) is a black pigment.
The polymerizable composition according to any one of claims 1 to 3, wherein the alkali developable compound (C) is an alkali developable compound represented by the following general formula (II).

(Wherein, R 11 , R 13 and R 15 each independently represent a hydrogen atom or a methyl group, and R 12 , R 14 and R 16 each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a complex) Represents a group having 2 to 20 carbon atoms containing a ring,
When a plurality of R 13 and R 14 exist, they may be the same or different,
Y 1 , Y 2 and Y 3 each represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocycle,
When two or more Y 2 exist, they may be the same or different,
Z 1 , Z 2 and Z 3 each represent a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
When two or more Z 2 exist, they may be the same or different,
The hydrogen atom in the group represented by R 12 , R 14 , R 16 , Y 1 , Y 2 , Y 3 , Z 1 , Z 2 and Z 3 is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, It may be substituted by a group having 2 to 20 carbon atoms containing a carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, mercapto group, isocyanate group or heterocyclic group, and R 12 , R 14 and R 16 And methylene groups in the groups represented by Y 1 , Y 2 , Y 3 , Z 1 , Z 2 and Z 3 are —O—, —CO—, —COO—, —OCO—, —S— or —SO 2- , -SCO- or -COS- may be substituted,
n represents a positive number of 0 or 10 or less, a represents a positive number of 0 or 4 or less, b represents a positive number of 0 or 3 or less, and c is a positive number of 0 or 4 or less Represents the number of
When n is 2 or more, b may be the same or different. )
A photosensitive composition for a black matrix comprising the polymerizable composition according to any one of claims 1 to 4.
A photosensitive composition for a black column spacer comprising the polymerizable composition according to any one of claims 1 to 4.
A polymerizable composition according to any one of claims 1 to 4, a photosensitive composition for a black matrix according to claim 5, or a photosensitive composition for a black column spacer according to claim 6 A method of producing a cured product by irradiation or heating.
A cured product of the polymerizable composition according to any one of claims 1 to 4, the photosensitive composition for a black matrix according to claim 5, or the photosensitive composition for a black column spacer according to claim 6.
A display apparatus comprising the cured product according to claim 8.