TW201906874A - Photosensitive composition, photosensitive composition for black matrix, and photosensitive composition for black column spacer - Google Patents

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 [alpha]-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 [alpha]-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 combination containing an α-aminoacetophenone compound having a hydroxyl group as a polymerization initiator, and further containing a colorant, an alkaline developing compound, and an ethylenically unsaturated compound other than the alkaline developing compound. Thing. The present invention relates to a photosensitive composition for a black matrix (hereinafter also referred to as "BM") and a black column spacer (hereinafter also referred to as "BCS") containing the composition, and a photosensitive composition for the same. A hardened product obtained from the composition.

In a display display device such as a liquid crystal display device or an organic EL display device, a spacer is used in order to maintain the distance between the upper part of the cell and the lower substrate.

The spacer is formed by applying a polymerizable composition to a substrate, developing it after exposure through a specific mask. In recent years, BCS which uses a column spacer and a black matrix in one module and has a light-shielding property has been used.

Patent Document 1 describes a photopolymerization initiator for a photosensitive solder resist containing an α-aminobenzophenone compound. Patent Document 2 describes a photosensitive resin composition for forming BCS, which contains carbon black subjected to a treatment for introducing an acidic group, and can form BCS having a low relative dielectric constant. Patent Document 3 describes a colored photosensitive resin composition containing a copolymer, an epoxy resin compound or a compound derived therefrom, and a coloring agent containing a black coloring agent and a blue coloring agent. BCS with flexible response rate. [Prior Art Literature] [Patent Literature]

[Patent Literature 1] Japanese Patent Laid-Open Publication No. 2016-090857 [Patent Literature 2] Japanese Patent Laid-Open Publication No. 2015-093986 [Patent Literature 3] Japanese Patent Laid-Open Publication No. 2014-146029

The problem to be solved by the present invention is that there is currently no hardened material (especially BCS) with excellent elastic response, excellent light-shielding properties, chemical resistance, low dielectric constant, and good electrical properties.

Therefore, an object of the present invention is to provide a polymerizable composition, a photosensitive composition for BM, and a photosensitive property for BCS, which can obtain a cured product having excellent elastic recovery, excellent light-shielding properties, chemical resistance, low dielectric constant, and good electrical properties. combination. Another object of the present invention is to provide a cured product obtained from the polymerizable composition, the photosensitive composition for BM, and the photosensitive composition for BCS, a display device including the cured product, and a method for manufacturing the cured product. method.

As a result of earnest research conducted by the present invention, the above-mentioned object is achieved by providing the following [1] to [9].

[1] A polymerizable composition containing a polymerization initiator (A), a colorant (B), an alkaline developable compound (C), and an ethylenic compound other than the alkaline developable compound (C) A polymerizable composition of a saturated compound (D), wherein the polymerization initiator (A) contains an α-aminoacetophenone compound (A1) having a hydroxyl group.

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

[Chemical 1] (In the formula, 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 heterocyclic group containing 2 to 20 carbon atoms. The hydrogen atom in the group represented by R ¹ and R ² passes through a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amine group, a carboxyl group, a methacryl group, an acryl group, an epoxy group, a vinyl group, and a vinyl ether group. In the case of substitution with a mercapto group, an isocyanate group, or a group containing 2 to 20 carbon atoms containing a heterocyclic ring, and the methylene group in the group represented by R ¹ and R ² is substituted with -O-, -CO -, -COO-, -OCO-, -NR ^3- , -NR ³ CO-, -S-, -CS-, -SO _2- , -SCO-, -COS-, -OCS-, unsaturated bond or In the case of CSO-, R ³ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, m represents 0 or 1, and * in the formula represents a bonding 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 alkaline developable compound (C) is an alkaline developable compound represented by the following general formula (II);

[Chemical 2] (In the formula, 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 carbon atom containing a heterocyclic ring. The base is a number of 2 to 20. When there are a plurality of cases of R ¹³ and R ¹⁴ , the same situation exists and there are different situations. Y ¹ , Y ^2, and Y ³ represent direct bonds, and the number of carbon atoms is 1 to 20. In the case of a hydrocarbon group or a heterocyclic-containing carbon group having 2 to 20 carbon atoms, when there are a plurality of Y ² , there are the same situations and different situations. Z ¹ , Z ² and Z ³ represent the number of carbon atoms as In the case of a hydrocarbon group of 1 to 20 or a group of 2 to 20 carbon atoms containing a heterocyclic ring, when there are a plurality of Z ² , there are the same cases and different cases. There are R ¹² , R ¹⁴ , R ¹⁶ , The hydrogen atom in the group represented by Y ¹ , Y ² , Y ³ , Z ¹ , Z ² and Z ³ passes a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amine group, a carboxyl group, a methacryl group, and acryl group. In the case of the substitution of an alkyl group, an epoxy group, a vinyl group, a mercapto group, an isocyanate group or a group containing a heterocyclic ring, and there are also R ¹² , R ¹⁴ , R ¹⁶ , Y ¹ , Y ² , Y ³ , Z represents a group of the ^1, Z ² and Z ³ in the methylene group is replaced by -O -, - CO -, - COO -, - OCO -, - S -, - SO 2 -, - SCO- or In the case of -COS-, n is a positive number below 0 or 10, a is a positive number below 0 or 4, b is a positive number below 0 or 3, and c is a positive number below 0 or 4, when n is 2 or more , B exists in the same situation and there are different situations).

[5] A photosensitive composition for a 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] A method for producing a cured product, using the polymerizable composition according to any one of [1] to [4], the photosensitive composition for a black matrix according to [5], or the black composition according to [6] A method for producing a cured product by irradiating or heating a photosensitive composition for a column spacer.

[8] A hardened product, which is a polymerizable composition according to any one of [1] to [4], a photosensitive composition for a black matrix such as [5], or a black column spacer such as [6] A cured product of a photosensitive composition.

[9] A display device including a hardened body as in [8].

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

The polymerizable composition of the present invention contains an α-aminoacetophenone compound having a hydroxyl group as a polymerization initiator, a colorant, a basic developing compound, and an ethylenically unsaturated compound other than the basic developing compound. Hereinafter, each component is demonstrated sequentially.

<Polymerization initiator (A)> The polymerization initiator (A) used in the polymerizable composition of the present invention contains an α-aminoacetophenone compound (A1) having a hydroxyl group [hereinafter also referred to as (A1) Component], and a radical polymerization initiator other than the previously known (A1) component may be used in combination.

The radical polymerization initiator is a photo radical polymerization initiator and a thermal radical polymerization initiator. Considering high self-reactivity, a photoradical polymerization initiator is more preferable.

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-based compounds, benzophenone-based compounds, Benzophenone compounds, 9-oxosulfur As the compound, an oxime ester compound and the like are preferable.

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

[Chemical 3] (In the formula, X _r represents the structure represented by the following general formula (i), (ii), or (iii), X _s represents a sulfur atom or NR ¹⁰⁰ , and R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² , R ^103, and R ¹⁰⁴ Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an aralkyl group having 7 to 20 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, and the alkyl group has a hydroxyl group , Carboxyl group, halogen atom, cyano group or nitro group, and the phenyl group and the aralkyl group are substituted by alkyl group having 1 to 4 carbon atoms, hydroxyl group, carboxyl group, halogen atom, cyano group or nitro group In some cases, R ¹⁰¹ and R ^{102 are} linked to form a heterocyclic ring of 3 to 6 members, and a nitrogen atom in the heterocyclic ring is bound to R ⁹⁹ , and R ¹⁰³ and R ^{104 are} linked. When a 3- to 6-membered ring is formed, 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. , the presence of the alkyl group substituted by a halogen atom, a carboxyl group, a cyano group, a nitro group or a hydroxyl case, R ⁹⁹ represents a hydrogen atom, an alkyl group having carbon atoms of 1 to 12, phenyl, carbon atoms, An aralkyl group having 7 to 20 or an alkenyl group having 2 to 12 carbon atoms, 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 aryl group may be present. The alkyl group may be substituted by 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. When substituted with -O-, -S-, -NR ^117- , -CO-, -CO-O-, -O-CO-, or -O-CO-O-. R ¹¹⁷ represents a hydrogen atom, the number of carbon atoms An alkyl group, phenyl group, aralkyl group having 7 to 20 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, and the alkyl group exists through a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, or a nitrate And the phenyl group and the aralkyl group are 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. (The compound represented has at least one hydroxyl group in the molecule)

[Chemical 4] (In the formula, R ¹⁰⁹ and R ¹¹⁰ each independently represent a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. When p is 2 or more, they may be the same or different. Of the following (i-1)

[Chemical 5] The methylene group in the structure represented may also be substituted with -O-, -S-, -NR ¹¹⁷ , -CO-, -CO-O-, -O-CO- or -O-CO-O-, R ¹¹¹ represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, an amine group, or a phenyl group, and the phenyl group is 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 In the case, p represents a number from 1 to 12)

[Chemical 6] (In the formula, 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, and the alkyl group is present. When the group is substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group, and the methylene group in the alkyl group is substituted with -O-, -S-, -NR ¹¹⁷ , -CO-, -CO-O- , -O-CO- or -O-CO-O-, there may be cases where R ¹⁰⁶ or R ¹⁰⁷ is bonded to R ¹¹² or R ¹¹⁶ to form a ring)

[Chemical 7] (Wherein R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ are the same as the general formula (V), and R ¹⁰⁹ , R ¹¹⁰ and p are the same as the general formula (i) the same)

Examples of the alkyl group having 1 to 12 carbon atoms as described above as the description of the general formula (V) include, for example, examples of the hydrocarbon group having 1 to 20 carbon atoms in the following general formula (I) The number of carbon atoms in the alkyl group having 1 to 20 carbon atoms is 1 to 12.

As the description of the general formula (V), each of the alkyl groups having 1 to 4 carbon atoms described above can be exemplified as a hydrocarbon group having 1 to 20 carbon atoms in the following general formula (I). As the alkyl group having 1 to 20 carbon atoms, the number of carbon atoms in the latter group is 1 to 4.

Examples of the aralkyl group having 7 to 20 carbon atoms as the description of the general formula (V) include, for example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl , Phenylethyl, etc.

Examples of the alkenyl group having 2 to 12 carbon atoms described above as the description of the general formula (V) include vinyl, 1-propenyl, 2-propenyl, isopropenyl, and 1-butene. Groups such as methyl, 2-butenyl, 3-butenyl, 1-octenyl, and 1-decenyl.

As the heterocyclic ring having 3 to 6 members which R ¹⁰¹ and R ¹⁰² in the general formula (V) can be linked to each other, for example, a piperidine ring, a piperidine ring, a phosphonium ring, a linacline ring, and the like are preferably mentioned.

As the 3- to 6-membered ring that R ¹⁰³ and R ¹⁰⁴ in the general formula (V) can be linked to form, for example, a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a lactone ring, an internal Amine ring and so on.

As a ring in which R ¹⁰⁶ or R ¹⁰⁷ is bonded to R ¹¹² or R ¹¹⁶ in the general formula (V), a structure in which X _s and left and right adjacent benzene rings are combined may be exemplified by a carbazole ring or a thion ring , Dibenzothiophene ring.

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

As a preferable (A1) component, the following compound No. A1-1-11 is mentioned, for example.

[Chemical 8]

Examples of the acetophenone-based compounds other than the component (A1) include α-aminoacetophenone compounds and α-hydroxyacetophenone compounds which do not have a hydroxyl group.

Examples of the acetophenone-based compound other than the component (A1) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 4'-isopropyl 2-hydroxy-2-methylphenylacetone, 2-hydroxymethyl-2-methylphenylacetone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p- Dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidebenzylidene, 1-hydroxycyclohexylphenylketone 2-methyl-1- [4- (methylthio) phenyl] -2-olinylacetone-1, 2-benzyl-2-dimethylamino-1- (4-olinylphenyl ) -Butanone-1, benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether and 1- [4- (2-hydroxyethoxy) -phenyl] -2 -Hydroxy-2-methyl-1-propane-1-one and the like.

Examples of the benzodiazone-based compound include benzodiazone.

Examples of the benzophenone-based compound include benzophenone, methyl orthobenzoylbenzoate, Michelin, 4,4'-bisdiethylaminobenzophenone, 4, 4'-dichlorobenzophenone and 4-benzylidene-4'-methyldiphenyl sulfide.

As 9-oxysulfur Compounds, 9-oxysulfur 2-methyl-9-oxysulfur , 2-ethyl-9-oxysulfur , 2-chloro-9-oxysulfur , 2-isopropyl-9-oxysulfur , 2,4-diethyl-9-oxysulfur Wait.

Examples of the oxime ester compound include an oxime ester compound (A2) having a group represented by the general formula (I). The oxime ester compound can be used in combination with the component (A1) in the photoradical polymerization initiator. Since it has high sensitivity, 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 preferably an alkyl group having 1 to 20 carbon atoms and 2 carbon atoms Alkenyl group of -20, cycloalkyl group of 3 to 20 carbon atoms, cycloalkylalkyl group of 4 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, or 7 to 20 carbon atoms Aralkyl and the like. Since the sensitivity when used as a polymerization initiator (A) is considered good, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 3 to 10 carbon atoms are more preferable. A cycloalkyl group, a cycloalkylalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and the like.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, and the like. Isopentyl, third pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, third octyl, nonyl, isononyl, decyl, isodecyl, undecyl , Dodecyl, tetradecyl, hexadecyl, octadecyl and eicosyl. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, Isopentyl, third pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, third octyl, nonyl, isononyl, decyl, and isodecyl, and the like.

Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, and 2 -Hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl Alkenyl, 3-undecenyl, 4-dodecenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl, and 4,8,12-14 Carbotrienyl allyl and the like. Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, and 2 -Hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl and 4-decenyl Alkenyl, etc.

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. Examples include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydrocyclopentane Alkenes, bicyclic [1.1.1] pentyl and tetradecahydroanthracenyl, etc. Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and adamantane. Alkyl, decahydronaphthyl, octahydrocyclopentadiene and bicyclic [1.1.1] pentyl, etc.

The above-mentioned cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group. Examples include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2 -Cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecyl Ethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-cyclononylpropyl , 3-cyclodecylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, 4-cycloheptylbutyl, 4-cyclooctylbutyl, 4- Cyclononylbutyl, 4-cyclodecylbutyl, 3-adamantylpropyl and 3-decahydronaphthylpropyl. Examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, and cyclooctyl. Methyl, cyclononylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 3- Cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl and 4-cyclohexylbutyl Base etc.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, or the like, or one or more of the above alkyl groups. Phenyl, biphenyl, naphthyl, anthracenyl, etc. substituted with the above alkenyl or carboxyl groups, halogen atoms, etc., such as 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methyl Phenyl, 2,4,6-trimethylphenyl and the like. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, or one or more of the alkyl group, the alkenyl group, or the carboxyl group. Phenyl, biphenyl, naphthyl, anthracenyl, etc. substituted with halogen atoms, such as 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4 , 6-trimethylphenyl and the like.

The above-mentioned aralkyl group having 7 to 20 carbon atoms means that a hydrogen atom of an alkyl group is substituted with an aryl group having 6 to 19 carbon atoms in the aryl group having 6 to 20 carbon atoms and has 7 to 20 A base of carbon atoms. Examples include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, and naphthylpropyl. The above-mentioned aralkyl group having 7 to 10 carbon atoms means that a hydrogen atom of an alkyl group having 7 to 10 is substituted with an aryl group having 6 to 9 carbon atoms in the aryl group having 6 to 20 carbon atoms. Examples of the carbon atom group include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, and phenylethyl.

When a heterocyclic-containing carbon atom group having 2 to 20 carbon atoms represented by R ¹ and R ² in the above-mentioned general formula (I) and a hydrogen atom in a radical represented by R ¹ and R ² are substituted The group containing 2 to 20 carbon atoms containing a heterocyclic ring is not particularly limited, and examples thereof include pyrrolyl, pyridyl, pyridylethyl, pyrimidinyl, daphyl, piperidyl, piperidinyl, and pyranyl , Pyranylethyl, pyrazolyl, triyl, triylmethyl, pyrrolidinyl, quinolinyl, isoquinolinyl, imidazolyl, benzimidazolyl, triazolyl, furyl, Furanyl, benzofuranyl, thienyl, thiophenyl, benzothienyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl , Isothiazolyl, isoxazolyl, indolyl, phosphono, thiolineno, 2-pyrrolidinone-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazole Pyridin-3-yl and 2,4-dioxyoxazolidin-3-yl and the like are specifically described as including a substituent and the like, and examples thereof include groups having the following structures.

[Chemical 9] (In the above formula, 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. In addition, as * in the formula, (The basis represented by this equation is the bond part with *.)

Examples of the alkyl group having 1 to 6 carbon atoms represented by R in the above formula include those having 1 to 6 carbon atoms as examples of the alkyl group having 1 to 20 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms represented by Z in the above formula include methylene, ethylidene, propylidene, methylidene, butyl, and 1-methyl. Butyl, 2-methyl butyral, 1,2-dimethyl butyral, 1,3-dimethyl butyral, 1-methyl butyl, 2-methyl butyl, Linear or branched chains such as 3-methyl-butylene, 4-methyl-butylene, 2,4-dimethyl-butylene, 1,3-dimethyl-butylene, pentyl, and hexyl Of extension alkyl.

Examples of each halogen atom described in the comments of the general formulae (I) and (III) include fluorine, chlorine, bromine, and iodine.

In the present specification, as an unsaturated bond in the case where the methylene group in the group described in the comment of each general formula (I) or (IV) is substituted, -C = C-, -C≡C -Wait.

Among the compounds having a group represented by the general formula (I), a compound represented by the following general formula (III) is preferred, and its sensitivity is particularly high, and therefore it can be used in the polymerizable composition of the present invention.

[Chemical 10] (Wherein, R ^1, R ^2, and m, R ² the same as m, R ²¹ and R ²² each independently represent a hydrogen atom, a nitro group, a cyano group, respectively, the general formula (I), R ¹ and the carbon atom An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a carbon group having 2 to 20 carbon atoms containing a heterocyclic ring, X ¹ represents an oxygen atom , Sulfur atom, selenium atom, CR ²³ R ²⁴ , CO, NR ²⁵ or PR ²⁶ , X ² represents a non-bonded, direct bond, hydrocarbon group having 1 to 20 carbon atoms, CO, and R ²³ to R ²⁶ are each independently Represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocyclic-containing carbon group having 2 to 20 carbon atoms, and a hydrogen atom in the group represented by R ²¹ to R ²⁶ also exists through a halogen atom or a nitro group. , Cyano, hydroxy, carboxyl or heterocyclic groups, there are also cases where the methylene group in the group represented by R ²¹ to R ²⁶ is substituted with -O- or -CO- under the condition that oxygen is not adjacent. There are also cases where R ²¹ to R ²⁶ each independently form an integral ring with an adjacent benzene ring, g represents a number of 0 to 4, and h represents a number of 0 to 3).

A hydrocarbon group having 1 to 20 carbon atoms represented by R ²³ to R ²⁶ in the general formula (III) and a hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ³ in general formula (I) the same. Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by X ² in the general formula (III) include those having 1 to 20 carbon atoms represented by R ¹ to R ³ as the general formula (I). It is a divalent group obtained by removing one hydrogen atom from each of the listed hydrocarbon groups. The alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the aralkyl group having 7 to 20 carbon atoms represented by R ²¹ and R ²² in the general formula (III), respectively Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ³ are the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the carbon atom The number of aralkyl groups of 7 to 20 is the same as that described above.

The heterocyclic-containing carbon atom group represented by R ²¹ to R ²⁶ in the general formula (III) and the heterocyclic-containing carbon atom group represented by R ¹ and R ² are 2 to 20 carbon atoms. The same base.

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

[Chemical 11]

[Chemical 12]

Examples of other radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzylidene diphenylphosphine oxide, and bis (cyclopentadienyl) -bis [2,6 -Difluoro-3- (pyrrole-1-yl)] titanium-locene compounds such as titanium.

Examples of commercially available free radical initiators include: Adeka Optomer N-1414, N-1717, N-1919, ADEKA ARKLS NCI-831, NCI-930 (the above are manufactured by ADEKA); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE784 (above manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (above manufactured by TRONLY), etc. .

The thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and previously known compounds can be used, and examples thereof include azo compounds, peroxides, and persulfates. Better.

Examples of the azo-based compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (isobutyric acid methyl ester), and 2,2'-azobis-2,4- Dimethylvaleronitrile, 1,1'-azobis (1-acetamido-1-phenylethane), and the like.

Examples of the peroxide include benzamidine peroxide, di-tert-butyl benzamidine peroxide, tert-butyl pervalerate, and di (4-tert-butyl ring peroxydicarbonate). Hexyl ester) and the like.

Examples of the persulfate include persulfate such as ammonium persulfate, sodium persulfate, and potassium persulfate.

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

In the general formula (III), when X ¹ is a sulfur atom and X ^{2 is} not bonded, it becomes, for example, an oxime ester system having a diphenyl sulfide skeleton represented by the aforementioned compounds Nos. A2-1 to A2-7. The compound is preferred in that a polymerizable composition having a good sensitivity can be obtained by using it in combination as a polymerization initiator.

In the general formula (III), when X ¹ is NR ⁵⁵ and X ² is a direct bond, it becomes an oxime ester compound having a carbazole skeleton represented by the aforementioned compound Nos. A2-8 to A2-14, It is especially preferable at the point which can obtain a polymerizable composition with favorable sensitivity.

The above-mentioned polymerization initiator (A) may be used singly as exemplified so far, or two or more thereof may be used in combination.

In the polymerizable composition of the present invention, the content of the polymerization initiator (A) is not particularly limited, and it is relative to the polymerization initiator (A), the colorant (B), the alkaline developing compound (C), and The total amount of the ethylenically unsaturated compound (D) is preferably from 0.1 to 20 parts by mass, more preferably from 0.3 to 10 parts by mass, and even more preferably from 0.3 to 5 parts by mass from the viewpoint of good hardenability in terms of 100 parts by mass in total. When the content of the polymerization initiator (A) is within the above range, it is preferable to obtain a polymerizable composition that has good curability and is excellent in storage stability without accompanying precipitation of the polymerization initiator. For example, when a hardened film having a thickness of 2 to 5 μm is formed, the content of the polymerization initiator (A) is not particularly limited, and it is relative to the polymerization initiator (A), the colorant (B), and the alkaline developability. The total of 100 parts by mass of the compound (C) and the ethylenically unsaturated compound (D) is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 0.3 to 5 parts by mass. In addition, from the viewpoints of elastic resilience, dielectric constant, and electrical characteristics, the proportion of the component (A1) in the polymerization initiator (A) is preferably 30% by mass or more, and more preferably 50% by mass or more. 85 Mass% or less. When the component (A1) is used in combination with a compound having a base represented by formula (I), the mass ratio of the component (A1): a compound having a base represented by formula (I) (the former: the latter) is smaller than It is preferably 2 to 5: 1, and more preferably 2 to 3: 1.

<Colorant (B)> As the coloring agent (B) used in the polymerizable composition of the present invention, a pigment or a dye can be used. As the pigment and the dye, an inorganic colored material or an organic colored material can be used, respectively. These can be used alone or in combination of two or more. Here, the term "pigment" means a coloring agent that is insoluble in a solvent to be described later, and also includes those that are insoluble in solvents in inorganic or organic colored materials, or those that have been inorganic-organic dyed.

Examples of the pigment include carbon black obtained by a furnace method, a trough method, or a thermal cracking method, or carbon black such as acetylene black, Ketjen black, or lamp black; and the carbon black is adjusted or covered by an epoxy resin. Those obtained by dispersing the carbon black in a solvent in advance and coating the resin with 20 to 200 mg / g of resin; those obtained by subjecting the carbon black to an acidic or alkaline surface treatment; average particle size Carbon black with a diameter of 8 nm or more and DBP oil absorption of 90 ml / 100 g or less; the total oxygen amount calculated from the CO and CO ₂ in the volatile matter at 950 ° C relative to a surface area of 9 mg per 100 m ² Carbon black; Graphitized carbon black, graphite, activated carbon, carbon fiber, carbon nanotube, carbon micro-coil, carbon nanohorn, carbon aerogel, fullerene, aniline black, pigment black 7. Black pigments represented by titanium black, melamine black and perylene black; chrome oxide green, milori blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate ultramarine blue, iron blue, ultramarine blue , Sky blue, strong green, emerald green, lead sulfate, yellow dan, zinc yellow, iron dan (red iron (III) oxide), cadmium red, To iron black, umber, organic lake pigments and inorganic pigments.

Among the above pigments, black pigments are preferred because of their high light-shielding properties, and organic black pigments such as osmamine and osmium black are more preferred in view of low liquid crystal contamination.

As the pigment, a commercially available product may be used, and examples thereof include pigment red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, and 97. , 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 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, 95, 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; pigments Purple 1, 19, 23, 27, 29, 30, 32, 37, 40, and 50.

Examples of the dye include a nitroso compound, a nitro compound, an azo compound, a diazo compound, Compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindolin compounds, quinacridone compounds, anthracene anthracene compounds, fluorene compounds , Fluorene compound, pyrrolopyrrole dione compound, thioindigo compound, difluorene compound, triphenylmethane compound, quinophthalone compound, naphthalenetetracarboxylic acid, azo dye, cyanine dye metal complex, and the like.

In the polymerizable composition of the present invention, the content of the colorant (B) is not particularly limited, and it is preferably 10 to 500 parts by mass, more than 100 parts by mass of the basic developing compound (C) described below. It is preferably 10 to 300 parts by mass, and more preferably 10 to 200 parts by mass. When the content of the colorant (B) is within the above range, the polymerizable composition is excellent in storage stability without accompanying colorant agglomeration, and the light-shielding property of the hardened material of the polymerizable composition is high. . For example, when a hardened material having a thickness of 1 to 3 μm is formed, the content of the colorant (B) is not particularly limited, and it is preferably 10 to 500 masses relative to 100 mass parts of the alkaline developable compound (C). Parts, more preferably 10 to 300 parts by mass, and even more preferably 10 to 200 parts by mass.

<Alkali developable compound (C)> The alkali developable compound (C) of this invention is a compound which has a hydrophilic group and shows alkali developability. In the present invention, as the basic developable compound (C), if the above-mentioned conditions are satisfied, a previously used compound can be used. Examples of the hydrophilic group include a hydroxyl group, a thiol group, a carboxyl group, a sulfo group, an amine group, an amido group, or a salt thereof. The hydroxyl group and the carboxyl group have high developability in an alkali because of the alkali developable compound (C). And better. The preferred functional group equivalent of the hydrophilic group in the alkaline developing compound (C) (the mass of the polymer compound containing 1 equivalent of the hydrophilic group) is 50 to 10,000. The preferred molecular weight of the alkaline developable compound (C) is a weight average molecular weight of 2,000 to 10,000, particularly preferably 3,000 to 6,000. The number average molecular weight is from 1,000 to 8000, especially from 2000 to 5,000. When the molecular weight of the alkaline developable compound (C) is in the above range, it is preferable to obtain a hardened material having excellent developability and excellent chemical resistance.

The acid value of the basic developing compound (C) is preferably 10 to 200 mg / KOH, and more preferably 30 to 150 mg / KOH. If the acid value is less than 10 mg / KOH, the alkaline developability may not be sufficiently obtained, and if it is more than 200 mg / KOH, the production of a polymer compound may be difficult. Here, the acid value is based on JIS K 0050 and JIS K 0211.

As the alkali developable compound (C), specifically, a compound represented by the above-mentioned general formula (II) and an acrylic ester copolymer; a phenol-based and / or cresol novolac epoxy resin; and a polyfunctional ring Epoxy polyphenylmethane type epoxy resin; epoxy acrylate resin; epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the following general formula (IV) ; A resin (unsaturated compound) having a structure obtained by an esterification reaction; the above-mentioned esterification reaction has a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the following general formula (IV); Esterification of epoxy addition compounds with polybasic acid anhydrides.

[Chemical 13] (In the formula, M ⁴ represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -O-, -S-, -SO _2- , -SS-, -SO-, -CO-, -OCO- Or a substituent of the group represented by the following formula (a), (b), (c) or (d), a hydrogen atom in a hydrocarbon group having 1 to 20 carbon atoms represented by M ⁴ is substituted with a halogen atom In the case, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ (hereinafter also referred to as “R ³¹ to R ³⁸ ”) each independently represent a hydrogen atom and a carbon atom number as For a hydrocarbon group of 1 to 20 or a halogen atom, k is a number of 0 to 10, and in the case of k ≧ 1, there are a plurality of R ³¹ to R ³⁸ and M ⁴ in the same case, and there are also different cases)

[Chemical 14] (In the formula, R ³⁹ represents a hydrocarbon group having 1 to 20 carbon atoms, and 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 ") each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group containing 2 to 20 carbon atoms, or a halogen atom In some cases, the methylene group in the group represented by R ³¹ to R ³⁸ and R ⁴⁰ to R ⁶⁸ is substituted with an unsaturated bond, -O- or -S-, and R ⁴⁰ and R ⁴¹ , R ⁴¹ and R are present. 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 , When 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 are} bonded to form a ring, (a), (b) (* In the bases represented by (c) and (d) represents a bonding bond)

By using the alkaline developable compound represented by the said general formula (II), since the hardened | cured material obtained from a polymerizable composition is excellent in chemical resistance, it is preferable.

If an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the general formula (IV) is used, or as an esterification reaction (the esterification reaction is The basic developable compound of the reaction product obtained by adding an epoxy addition compound having a structure of an unsaturated monobasic acid to an epoxy compound represented by the formula (IV) and an esterification reaction of a polybasic acid anhydride) is a polymerizable combination The sensitivity of the material is high, and the cured product obtained from the polymerizable composition is excellent in elastic recovery rate, and is therefore preferred.

Since the dispersibility of the colorant (B) is improved and the heat resistance is good, the basic developable compound (C) is preferably an epoxy compound represented by the general formula (IV); An epoxy compound having the following structure [(e)], which is obtained by adding an unsaturated monoacid to the represented epoxy compound; or having the following structure obtained by an esterification reaction of the unsaturated compound and a polybasic acid anhydride: Unsaturated compound of structure [(f)].

[Chemical 15] (In the formula, Y ⁷ represents a residue of an unsaturated monobasic acid, Y ⁸ represents a residue of a polybasic acid anhydride, and * represents a bonding bond)

In the case where M ⁴ is a base represented by (b) or (c) in the alkaline developable compound represented by the general formula (IV), the solvent resistance of the cured product obtained from the polymerizable composition Get better, so better.

Examples of 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 general formula (II) include the descriptions with the general formula (I) The above-mentioned hydrocarbon groups having 1 to 20 carbon atoms are the same.

A group having 2 to 20 carbon atoms containing a heterocyclic ring represented by R ¹² , R ¹⁴ , R ¹⁶ , Y ¹ to Y ³ and Z ¹ to Z ³ in the above-mentioned general formula (II), and R ¹² , When a hydrogen atom in a group represented by R ¹⁴ , R ¹⁶ , Y ¹ , Y ² , Y ³ , Z ¹ , Z ² and Z ³ is substituted, a group containing 2 to 20 carbon atoms containing a heterocyclic ring Examples of the same group as those having 2 to 20 carbon atoms in the heterocyclic-containing ring described in the description of the general formula (I) are mentioned.

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by M ⁴ and R ³¹ to R ⁶⁸ in the general formula (IV) include those having 1 to 20 carbon atoms described in the description of the general formula (I). The same hydrocarbyl group.

Examples of the heterocyclic-containing carbon atom group having 2 to 20 carbon atoms represented by R ⁴⁰ to R ⁶⁸ in the general formula (IV) include the heterocyclic-containing carbon groups described in the description of the general formula (I). Those having 2 to 20 atoms have the same base.

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

As 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 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 The ring formed by bonding ⁶⁷ and R ⁶⁸ includes, for example, cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine, pyrrole, piperidine, thioline, tetrahydropyridine, a lactone ring, and 5- to 7-membered rings such as the lactam ring and condensed rings such as naphthalene and anthracene.

The unsaturated monobasic acid is an acid having an unsaturated bond in the structure and having one hydrogen atom that can be ionized to become a hydrogen ion in one molecule. Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, butenoic acid, cinnamic acid, sorbic acid, and hydroxyethyl methacrylate-maleate, and hydroxypropyl methacrylate-maleate. , Hydroxypropyl acrylate-maleate and dicyclopentadiene-maleate.

Examples of the polybasic acid anhydrides that work after the unsaturated monobasic acid functions include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphenyltetracarboxylic dianhydride, and malay. Acid anhydride, trimellitic anhydride, pyromellitic dianhydride, 2,2'-3,3'-benzophenone tetracarboxylic dianhydride, ethylene glycol dianhydrotrimellitate, triglyceride trihydrate Triester, Hexahydrophthalic Anhydride, Methyltetrahydrophthalic Anhydride, Geo-Anhydride, Methyl Geodesic Anhydride, Trialkyltetrahydrophthalic Anhydride, Hexahydrophthalic Anhydride , 5- (2,5-Dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride addition Compounds, dodecenyl succinic anhydride, methylbicycloheptene dicarboxylic anhydride and the like.

The molar reaction of the epoxy compound, the unsaturated monobasic acid, and the polybasic acid anhydride is preferably set as follows. That is, it is preferable that the epoxy addition compound is added at a ratio of 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid relative to one epoxy group of the epoxy compound, and that the reaction is The product is preferably a ratio of 0.1 to 1.0 of the anhydride structure of the polybasic acid anhydride with respect to one hydroxyl group of the epoxy adduct. The reaction of the epoxy compound represented by the general formula (IV), the unsaturated monobasic acid, and the polybasic acid anhydride can be carried out in accordance with conventional practices.

In order to improve the developability of the polymerizable composition, the photosensitive composition for BM, and the photosensitive composition for BCS of the present invention in order to adjust the acid value, it may be further monofunctional or polyfunctional together with the basic developing compound (C). Functional epoxy compounds react. The acid value of the solid component of the basic developing compound (C) is preferably in the range of 5 to 120 mgKOH / g, and the amount of the monofunctional or polyfunctional epoxy compound is preferably selected in a manner to satisfy the acid value. .

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, and isopropyl ether. Butyl glycidyl ether, third butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, ten Monoalkyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, cetyl glycidyl ether, 2-ethyl Hexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether Ether, tolyl glycidyl ether, 2-methyltolyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether Glyceryl ether, methacrylic acid 2 , 3-epoxypropyl ester, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinyl cyclohexane monoxide, 1,2-epoxy-4-vinyl cyclohexane, epoxy Phenylethane, pinene oxide, methyl phenylene oxide, cyclohexane, propylene oxide, the following epoxy compounds No. E1, No. E2, and the like.

[Chemical 16]

[Chemical 17]

As the polyfunctional epoxy compound, it is preferable to use one or more compounds selected from the group consisting of a bisphenol-type epoxy compound and glycidyl ethers, since a polymerizable composition having further excellent characteristics can be obtained, and therefore, it is preferable. As the bisphenol type epoxy compound, in addition to the epoxy compound represented by the general formula (IV), for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound may be used. As the 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 (glycidyl Glyceryloxymethyl) propane, 1,1,1-tris (glycidyloxymethyl) ethane, 1,1,1-tris (glycidyloxymethyl) methane, 1,1,1,1 -Tetrakis (glycidyloxymethyl) methane and the like. In addition, phenolic novolac epoxy compounds, biphenol novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolacs Type epoxy compounds and other novolac type epoxy compounds; 3,4-epoxy-6-methylcyclohexanecarboxylic acid-3,4-epoxy-6-methylcyclohexylmethyl ester, 3,4-cyclo Alicyclic epoxy compounds such as oxycyclohexanecarboxylic acid-3,4-epoxycyclohexylmethyl ester, 1-epoxyethyl-3,4-epoxycyclohexane; diglycidyl phthalate , Glycidyl esters such as diglycidyl tetrahydrophthalate, glycidyl dimer acid; tetraglycidyl diamino diphenylmethane, triglycidyl p-aminophenol, N, N-di Glycidyl amines such as glycidyl aniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as cyclopentadiene; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; dicyclopentadiene type epoxy compounds and the like.

As the alkali developable compound (C), a commercially available product can also be suitably used. Examples of the commercially available products include SPC1000, SPC-2000, SPC-3000, SPRR-1X, SPRR-2X, SPRR-3X, SPRR-5X, SPRR-6X, SPRR-7X, SPRR-8X, and SPRR- 9X, SPRR-10X, SPRR-11X, SPRR-12X, SPRR-13X, SPRR-14X, SPRR-15X, SPRR-16X, SPRR-17X, SPRR-18X, SPRR-19X, SPRR-20X, SPRR-21X ( The above are manufactured by Showa Denko Corporation), JET2000, AGOR1060, AGOR3060, ORGA1060, ORGA2060 (the above are manufactured by Osaka Organic Chemical Co., Ltd.), CCR-1171H (made by 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, and it is relative to the polymerization initiator (A), the colorant (B), the alkali developable compound (C), and The total amount of the ethylenically unsaturated compound (D) is preferably 100 to 90 parts by mass, preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, and even more preferably 30 to 80 parts by mass. When the content of the alkaline developable compound (C) is within the above-mentioned range, the alkaline developability of the polymerizable composition is good, so it is preferable. For example, when a hardened film having a thickness of 2 to 5 μm is formed, the content of the alkaline developable compound (C) is not particularly limited, and it is relative to the polymerization initiator (A), the colorant (B), and the alkaline development. The total of 100 parts by mass of the sexual compound (C) and the ethylenically unsaturated compound (D) is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, and even more preferably 30 to 80 parts by mass. When the basic developable compound (C) contains a compound represented by the general formula (II), the amount is relative to the polymerization initiator (A), the colorant (B), and the basic developable compound (C). ) And the ethylenically unsaturated compound (D) in a total amount of 100 parts by mass, preferably 10 to 60 parts by mass, and more preferably 20 to 50 parts by mass. In addition, an epoxy addition compound (having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the general formula (IV)), or an epoxy addition compound and a polybasic acid anhydride is used. In the case of a reaction product obtained by an esterification reaction, the amount is 100 with respect to the total of the polymerization initiator (A), the colorant (B), the basic developing compound (C), and the ethylenically unsaturated compound (D). It is preferably 5 to 80 parts by mass, and more preferably 5 to 40 parts by mass. The content of the above-mentioned epoxy addition compound and the reaction product obtained by the esterification reaction of the epoxy addition compound with a polybasic acid anhydride, in the case where only one of the epoxy addition compound and the reaction product is contained When it is the amount, when it contains both, it is the total amount.

<Ethylene Unsaturated Compound (D)> The ethylenically unsaturated compound (D) used in the present invention is a compound which has an ethylenically unsaturated bond and is not the above-mentioned basic developing compound (C). Examples of the ethylenically unsaturated compound (D) include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (methyl) Acrylic acid, alpha-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, dicycloheptene dicarboxylic acid, butenoic acid, methacrylic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid , Mesaconic acid, succinic acid mono [2- (meth) acryloxyethyl], phthalic acid mono [2- (meth) acryloxyethyl], ω-carboxy polycaprolactone Mono (meth) acrylates such as polymers with carboxyl and hydroxyl groups at both ends; hydroxyethyl (meth) acrylate-maleate, hydroxypropyl (meth) acrylate- Unsaturated polybasic acids such as maleate, dicyclopentadiene-maleate or polyfunctional (meth) acrylates having one carboxyl group and two or more (meth) acrylfluorenyl groups; (meth) acrylic acid 2-hydroxyethyl ester, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, the following acrylic compounds No. 1 to No. 4, (meth) Methyl enoate, butyl (meth) acrylate, isobutyl (meth) acrylate, third butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, (meth) Dimethylaminomethyl acrylate, dimethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, (meth) acrylic acid Ethoxyethyl, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, benzene (meth) acrylate Ethoxyethyl ester, tetrahydrofuran (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, di Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butane Alcohol di (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, isocyanuric acid tri [(meth) propylene Unsaturated monobasic acids such as fluorenylethyl] esters, polyester (meth) acrylate oligomers, and esters of polyhydric alcohols or polyphenols; unsaturated polybasic acids such as zinc (meth) acrylate, and magnesium (meth) acrylate Metal salts; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2, 5-Dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecene Anhydrides of unsaturated polybasic acids such as methyl succinic anhydride, methylbicycloheptene dicarboxylic acid anhydride; (meth) acrylamide, methylenebis (meth) acrylamide, bis (ethyltriamine) tris (methyl) ) Acrylic Ammonium amine, xylylene bis (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and other unsaturated monoacids and polyamines; ammonium Unsaturated aldehydes, such as aldehydes; (meth) acrylonitrile, α-chloroacrylonitrile, dicyanethylene, allyl nitrile, and other unsaturated nitriles; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid Unsaturated aromatic compounds such as vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allyl amine, N-vinyl pyrrolidone, Unsaturated amine compounds such as vinyl piperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl shrink Vinyl ethers such as glycerin ether; Unsaturated fluorenimines such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; indene such as indene, 1-methylindene Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; polystyrene, poly (meth) acrylate, poly (meth) acrylate, polybutylene Siloxane and other macromonomers with a mono (meth) acrylfluorene group at the end of the polymer molecular chain; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, phosphoric acid Triallyl ester, triallyl isocyanurate, vinyl sulfide, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl monomer containing a hydroxyl group And polyisocyanate compounds, urethane compounds, vinyl monomers containing hydroxyl groups, and vinyl epoxy compounds of polyepoxides. The said ethylenically unsaturated compound (D) can be used individually or in mixture of 2 or more types.

As the ethylenically unsaturated compound, a commercially available product can also be used. Examples of the commercially available products include: Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, and R-684 (the above are manufactured by Nippon Kayaku Co., Ltd.); ARONIX M-215, M -350 (above manufactured by Toa Kosei); NK-ESTER A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, and HD-N (above manufactured by Shin Nakamura Chemical Industry Co., Ltd. ); SPC-1000, SPC-3000 (above manufactured by Showa Denko Corporation); NK-OLIGO U-4HA, U-4H, U-6HA, U-15HA, U-108A, U-1084A, U-200AX, U -122A, U-340A, U-324A, UA-53H, UA-100, AH-600 (above manufactured by Shin Nakamura Chemical Industry Co., Ltd.), UA-306H, AI-600, UA-101T, UA-101I, UA -306T, UA-306I (above manufactured by Kyoeisha Chemical Co., Ltd.), Artresin 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-907, UN-952, UN-953, UN-954, H-91, H-135 (The above are manufactured by Kone Industrial Corporation ), Sartomer CN968, CN975, CN989, CN9001, CN9010, CN9025, CN9029, CN9165, CN2260 (the above are manufactured by Sadobene Company), EBEC RYL8810 (manufactured by Daicel).

[Chemical 18]

[Chemical 19]

[Chemical 20]

[Chemical 21]

In the polymerizable composition of the present invention, the content of the ethylenically unsaturated compound (D) is not particularly limited, and it is relative to the polymerization initiator (A), the colorant (B), the alkaline developing compound (C), and The total amount of the ethylenically unsaturated compound (D) is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 5 to 20 parts by mass. When the content of the ethylenically unsaturated compound (D) is within the above range, the obtained hardened material is excellent in hardenability and light-shielding property, and therefore, it is preferable. For example, when a hardened film having a thickness of 1 to 3 μm is formed, the content of the ethylenically unsaturated compound (D) is not particularly limited, and it is relative to the polymerization initiator (A), colorant (B), and alkaline development. The 100% by mass of the total of the ethylenic compound (C) and the ethylenically unsaturated compound (D) is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and more preferably It is preferably 5 to 20 parts by mass.

A solvent may be further added to the polymerizable composition of the present invention. The solvent is usually a solvent that can dissolve or disperse the above components (polymerization initiator (A), colorant (B), basic developing compound (C), ethylenically unsaturated compound (D), etc.)) as necessary. Examples include: ketone solvents such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; Ether solvents such as ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-acetate Ester solvents such as propyl ester, isopropyl acetate, n-butyl acetate, 3-methoxybutyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and TEXANOL; ethylene glycol monomethyl ether and Cellulose solvents such as ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso-or-n-propanol, iso-n-butanol, and pentanol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, propylene glycol-1-monomethyl ether (PGM), propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and Ether-based solvents such as ethoxyethyl propionate; BTX-based solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; turpentine, D-limonene, and thallium Terpenes ; Paraffin solvents such as mineral spirits, Swasol # 310 (above manufactured by Cosmo Songshan Petroleum Company) and Solvesso # 100 (above manufactured by Exxon Chemical Company); carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and Halogenated aliphatic hydrocarbon solvents such as 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, dimethylsulfinium and water, etc. These solvents can be used alone or as a mixed solvent of two or more use.

Among these, ketone solvents, ester solvents, ether ester solvents, etc., especially cyclohexanone, 3-methoxybutyl acetate, dimethyl succinate, and PGMEA, etc. The compatibility between the agent and the polymerization initiator is good and preferred.

If PGMEA, 3-methoxybutyl acetate, and dimethyl succinate are used together, it is preferable to obtain a uniform coating surface, and the ratio based on the mass basis of the above solvent (PGMEA: 3-methoxybutyl acetate Ester: dimethyl succinate) is particularly preferred when it is 15 to 25: 2 to 5: 1.

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, and more preferably 50 to 95% by mass, based on 100% by mass of the total amount of the polymerizable composition. When the content of the solvent is in the above range, it becomes operability (viscosity or wettability of the polymerizable composition), reduction of unevenness during drying, and liquid stability (not accompanied by components contained in the composition It is preferable that the polymerizable composition having excellent precipitation or precipitation) is capable of appropriately controlling the thickness of the cured product when obtaining the cured product.

In the polymerizable composition of the present invention, 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, a sensitizer, Surfactants and thermal polymerization inhibitors such as melamine compounds, p-anisole, hydroquinone, catechol, tertiary butyl catechol, and phenanthrene; plasticizers; adhesion promoters; fillers; defoamers Agents; leveling agents; surface modifiers; antioxidants; ultraviolet absorbers; dispersion aids; anti-agglomerating agents; catalysts; effect promoters; cross-linking agents; tackifiers and other commonly used additives.

Examples of the epoxy compound include methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, C12 to 13 mixed alkyl glycidyl ether, and phenyl- 2-methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, glycidyl methacrylate, isopropyl glycidyl ether, allyl glycidyl ether, ethyl glycidyl ether, 2 -Methyl octyl glycidyl ether, phenyl glycidyl ether, 4-n-butylphenyl glycidyl ether, 4-phenylphenol glycidyl ether, tolyl glycidyl ether, dibromotolyl glycidyl ether, decyl Glycidyl ether, methoxy polyethylene glycol monoglycidyl ether, ethoxy polyethylene glycol monoglycidyl ether, butoxy polyethylene glycol monoglycidyl ether, phenoxy polyethylene glycol monoglycidyl ether Glyceryl ether, Dibromophenyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl Glycidyl ether, 1,1,2,2-tetrakis (glycidyloxyphenyl) ethane and pentaerythritol tetraglycidyl Ethers such as glycidyl ethers; glycidyl esters such as glycidyl acetate and glycidyl stearate; 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) rings Hexane-methyldioxane, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2 -Bis (3,4-epoxycyclohexyl) propane, ethylidene bis (3,4-epoxycyclohexanecarboxylate), adipic acid bis (3,4-epoxycyclohexylmethyl ester), 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester, 3,4-epoxy-1-methylhexanecarboxylic acid 3,4-epoxy-1-methylhexyl ester 6-methyl-3,4-epoxycyclohexanecarboxylic acid 6-methyl-3,4-epoxycyclohexylmethyl ester 3,4-epoxy-3-methylcyclohexanecarboxylic acid 3 1,4-epoxy-3-methylcyclohexylmethyl ester, 3,4-epoxy-5-methylcyclohexanecarboxylic acid Oxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, diepoxydicyclopentadiene, 3,4-epoxy-6-formaldehyde Cyclohexyl carboxylate, α-pinene oxide, phenylene oxide, epoxy cyclohexane, and epoxy cyclopentane, and other epoxy cycloalkyl compounds and N-glycidylphthalimide Amine, etc.

As the epoxy compound, an epoxidized polyolefin can also be used. The so-called epoxidized polyolefin is a polyolefin modified by an epoxy-containing monomer, and an epoxy-based polyolefin is introduced. It can be produced by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms, a monomer containing an epoxy group, and other monomers as necessary, by any method of a copolymerization method or a grafting method. Ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy-group-containing monomer, and other monomers may be polymerized individually or in combination with other monomers. In addition, it can also be obtained by epoxidizing the double bond of a non-conjugated polybutadiene having a hydroxyl group at its terminal by the peracetic acid method, and it can also be used in a molecule having a hydroxyl group. In addition, the hydroxyl group may be urethanized by isocyanate, and an epoxy compound containing a primary hydroxyl group may be reacted to introduce an epoxy group.

Examples of the ethylene or α-olefin having 3 to 20 carbon atoms include ethylene, propylene, butene, isobutylene, 1,3-butadiene, 1,4-butadiene, and 1,3-pentadiene. , 2,3-dimethyl-1,3-butadiene, pentadiene, 3-butyl-1,3-octadiene, isoprene, etc.

Examples of the epoxy-group-containing monomer include glycidyl esters of α, β-unsaturated acids, vinyl benzyl glycidyl ether, allyl glycidyl ether, and the like. Specific examples of the glycidyl ester of an α, β-unsaturated acid include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Particularly preferred is glycidyl methacrylate.

As the epoxy compound, a commercially available product may be used. Examples of suitable commercially available products include: Epolight 40E, 1500NP, 1600, 80MF, 4000, and 3002 (the above are manufactured by Kyoeisha Chemical Co., Ltd.); Adeka Glycilol ED-503, ED-503D, ED-503G, ED- 523T, ED-513, ED-501, ED-502, ED-509, ED-518, ED-529, Adeka Resin EP-4000, EP-4005, EP-4080, and EP-4085 (the above are manufactured by 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 manufactured by Nagase Kasei Corporation); EHPE-3150, Celloxide 2021P, 2081, 2000, and 3000 (Above manufactured by Daicel); EPIOL M, EH, L-41, SK, SB, TB, and OH (above manufactured by Nippon Oil Corporation); Epolight M-1230 and 100MF (above manufactured by Kyoeisha Chemical Co., Ltd.) ; ARONE OXETANE OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211 and OXT-212 (above manufactured by Toa Kosei); Etanacol OXBP and OXTP (above manufactured by Ube Kosan) ; 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether and 4-hydroxyl Butyl vinyl ether (manufactured by Maruzen Petrochemical Corporation); DENACOL EX-121, EX-141, EX-142, EX-145, EX-146, EX-147, EX-201, EX-203, EX-711 , EX-721, oncoat EX-1020, EX-1030, EX-1040, EX-1050, EX-1051, EX-1010, EX-1011 and 1012 (above manufactured by Nagase Kasei Corporation); OGSOL PG-100, EG-200, EG-210 and EG-250 (above manufactured by Osaka Gas Chemicals); HP4032, HP4032D and HP4700 (above manufactured by DIC); ESN-475V (manufactured by Toto Kasei Corporation); Marproof G-0105SA and G -0130SP (above manufactured by Nippon Oil); EPICLON N-665 and HP-7200 (above manufactured by DIC); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000 , EPPN-501H, EPPN-501HY, EPPN-502H and NC-7000L (the above are manufactured by Nippon Kayaku Co., Ltd.) and so on.

The above-mentioned alkaline developability imparting agent is a compound that does not have radical polymerizability and imparts alkaline developability. As such a compound, if it is a compound that is soluble in an alkaline aqueous solution because it has an acid value, it does not have In particular, as a representative compound, an alkali-soluble novolak resin (hereinafter referred to simply as "novolak resin") is mentioned. Novolac resins can be obtained by polycondensing phenols and aldehydes in the presence of an acid catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, and p-butylphenol , 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethyl Phenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2-methylresorcinol, catechol, α-naphthol, bisphenol A, dihydroxybenzoate, and phenol Gallic acid esters, etc. Among these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2,3,5- Trimethylphenol, resorcinol, 2-methylresorcinol and bisphenol A. These phenols can be used alone or in combination of two or more.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropanal, β-phenylpropanal, o-hydroxybenzaldehyde, and m-hydroxybenzene Formaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzene Formaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, and p-n-butylbenzaldehyde. Among these compounds, formaldehyde, acetaldehyde, and benzaldehyde are preferred. These aldehydes can be used alone or in combination of two or more. Aldehydes are preferably used at a ratio of 0.7 to 3 moles, particularly preferably 0.7 to 2 moles per mole of mols.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, oxalic acid, and acetic acid. The usage amount of these acid catalysts is preferably 1 × 10 ^-4 to 5 × 10 ^-1 mole per 1 mole of phenols. In the condensation reaction, water is usually used as the reaction medium, but the phenols used in the condensation reaction are not dissolved in the aqueous solution of aldehydes, and when the system becomes a heterogeneous system from the beginning of the reaction, hydrophilicity can also be used. The solvent serves as the reaction medium. Examples of such hydrophilic solvents include alcohols such as methanol, ethanol, propanol, and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media 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 according to the reactivity of the reaction raw materials, and is usually 10 to 200 ° C, preferably 70 to 150 ° C. After the condensation reaction is completed, in order to remove unreacted raw materials, acid catalysts and reaction media present in the system, the internal temperature is generally raised to 130-230 ° C, the volatiles are distilled off under reduced pressure, and the molten novolac is then removed. The resin is cast on a steel belt or the like and recovered. In addition, it can also be recovered by dissolving the reaction mixture in the above-mentioned hydrophilic solvent after the completion of the condensation reaction and adding it to a precipitant such as water, n-hexane, and n-heptane to thereby precipitate the novolac resin, The precipitate was separated and dried by heating.

Examples other than the above-mentioned novolak resin include polyhydroxystyrene or a derivative thereof, a styrene-maleic anhydride copolymer, and a polyhydroxybenzoate.

The dispersant may be any one that can disperse and stabilize the colorant (B), and a commercially available dispersant such as BYK series manufactured by BYK-Chemie can be used. Polymeric dispersant of basic functional polyester, polyether, polyurethane, with nitrogen atom as basic functional group, functional group with nitrogen atom is amine and / or its quaternary salt, amine value It is 1 ～ 100 mgKOH / g.

The above-mentioned latent additive is inert at normal temperature, light exposure step and pre-baking step, and is protected by heating at 100 to 250 ° C or heating at 80 to 200 ° C in the presence of an acid / base catalyst. Base detached and activated. Examples of the effects obtained by activation include oxidation resistance, ultraviolet absorption, antifouling properties, recoatability, and adhesiveness. As the latent additive, those described in WO2014 / 021023 can be preferably used.

As the latent additive, a commercially available product can be used, and examples thereof include ADEKA ARKLS GPA-5001 and the like.

Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, and 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, polyurethane resin, polymer Carbonate, polyvinyl butyral, cellulose ester, polypropylene ammonium, saturated polyester, phenol resin, phenoxy resin, polyamidamine imine resin, polyamino acid resin, epoxy resin, etc. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferable. The properties of the cured product can also be improved by using the organic polymer together with the basic developable compound (C). When using an organic polymer, the usage-amount is 10-500 mass parts with respect to 100 mass parts of said alkaline developable compounds (C).

Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silicon oxide, and aluminum oxide; layered clay minerals, and Milo Blue, calcium carbonate, magnesium carbonate, cobalt-based, manganese-based, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicates, calcium silicates, hydroxides Aluminum, platinum, gold, silver, copper, and the like are preferred, among which titanium oxide, silicon oxide, layered clay minerals, and silver are preferred.

Since the polymerizable composition of the present invention contains an inorganic compound, it can be used as a photosensitive paste composition. The photosensitive paste composition is used to form baked product patterns such as a partition wall pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel. These inorganic compounds can also be used as fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.

When an inorganic compound is added to the polymerizable composition of the present invention, the content of the inorganic compound is preferably from 0.1 to 50 parts by mass, more preferably from 0.5 to 100 parts by mass of the basic developing compound (C). 20 parts by mass of these inorganic compounds may be used alone or in combination of two or more.

Examples of the coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, and methyltrimethoxy Alkyl functional alkoxysilanes such as methylsilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltrimethoxysilane Alkenyl functional alkoxysilanes such as ethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethyl (Meth) acrylate functional alkoxysilanes such as oxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3 Epoxy-functional alkoxysilanes such as 1,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, N -β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and other amine groups Mercapto-functional alkoxysilanes such as functional alkoxysilane, γ-mercaptopropyltrimethoxysilane, isocyanate-functional alkoxysilanes such as 3-isocyanatepropyltriethoxysilane, 3-ureido Urea-based alkoxysilanes such as propyltrialkoxysilane, isocyanurate-functional alkoxysilanes such as tris (trimethoxysilylpropyl) isocyanurate, tetraisopropanol Titanium alkoxides such as titanium and titanium tetra-n-butoxide, titanium octyl bis (octanediol), titanium diisopropoxy bis (ethyl ethyl acetate), and tetraethylacetone Zirconium chelates such as zirconium acid, zirconium tributoxymonoethylfluorenylpyruvate, zirconium halides such as zirconium tributoxymonostearate, isocyanate silanes such as methyltriisocyanate silane and the like. The addition of a coupling agent is preferred because the adhesion between the cured product and the substrate (especially glass) can be improved.

As the coupling agent, commercially available products can be used, and examples thereof include KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, and 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-103 , HMDS-3, KBM-3063, KBM-3103C, KPN-3504, and KF-99 (the above are manufactured by Shin-Etsu Silicone).

As the chain transfer agent and sensitizer, a compound containing a sulfur atom is generally used. 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) aminomethane] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercapto (Propanyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercaptoethanol Mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto Thiol compounds such as 3-pyridyl alcohol, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris (3-mercaptopropionate), and pentaerythritol tetrakis (3-mercaptopropionate); Disulfide compounds obtained by oxidation, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid and 3-iodopropanesulfonic acid, iodoalkyl compounds; trimethylolpropane tri (3-mercapto Isobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, sebacylthiol, 1,4-dimethylmercaptobenzene, butanediol bismercaptan Propionate, Butanediol Dimercaptoacetate, Ethylene Glycol Dimercaptoacetate, Trimethylolpropane Trimercaptoacetate, Butanediol Dimercaptopropionate, Trimethylolpropane Trimercaptopropane Acid ester, trimethylolpropane trimercaptoacetate, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoacetate, trimercaptopropane trihydroxyethyl ester, the following compound No. C1, Karenz manufactured by Showa Denko Corporation PE-1 and NR1.

[Chemical 22]

The pattern of the hardened | cured material obtained by adding the said chain transfer agent and a sensitizer becomes high definition, Therefore, it is preferable.

As the surfactant, a fluorine surfactant such as a perfluoroalkyl phosphate, a perfluoroalkyl carbonate, or an anionic surfactant such as an alkali metal salt of a higher fatty acid, an alkyl sulfonate, or an alkyl sulfate can be used. , Cationic surfactants such as higher amine hydrohalates, quaternary ammonium salts, non-ionic interfaces such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides Surfactants such as active agents, amphoteric surfactants and silicone-based surfactants can also be used in combination.

Examples of the melamine compound include active hydroxyl groups in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. A compound in which all or a part (at least two) of methyl groups (CH ₂ OH groups) are alkylated. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other. In addition, the hydroxymethyl group which is not alkyl etherified may be self-condensed in one molecule, or may be condensed between two molecules, and as a result, an oligomer component is formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, and the like can be used. Among these, melamine having alkyl etherification such as hexamethoxymethylmelamine and hexabutoxymethylmelamine is preferred.

In the polymerizable composition of the present invention, an optional component other than a polymerization initiator (A), a colorant (B), an alkaline developing compound (C), an ethylenically unsaturated compound (D), a solvent, and an inorganic compound The content can be appropriately selected according to the purpose of use, and is not particularly limited as long as the effect of the present invention is not impaired. It is preferably based on the polymerization initiator (A), the colorant (B), and the alkaline developing compound. The total of 100 parts by mass of the total of (C) and the ethylenically unsaturated compound (D) is 20 parts by mass or less.

The photosensitive composition for BM of the present invention contains a polymerization initiator (A), a colorant (B), an alkaline developing compound (C), and an ethylenically unsaturated compound (D) as essential components. Alkali developability, especially suitable for BM-forming compositions.

The photosensitive composition for BCS of the present invention contains a polymerization initiator (A), a colorant (B), an alkaline developing compound (C), and an ethylenically unsaturated compound (D) as essential components. Alkali developability, especially suitable for forming BCS composition.

The polymerizable composition, the photosensitive composition for BM or the photosensitive composition for BCS, and the cured product of the present invention can be used for curable coatings, varnishes, curable adhesives, printed substrates, and display devices (color televisions, PC monitors, Color filters for 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, and electroluminescent display devices ( Micro LED partition wall material), plasma display panel, black partition wall of organic EL, powder coating, printing ink, printing plate, adhesive, gel coating, photoresist for electronics, plating resist , Etching resist, solder resist, insulating film, black matrix, and resist used to form structures in the manufacturing steps of LCDs, compositions for sealing electrical and electronic parts, solder resists, magnetic recording materials, Tiny mechanical parts, waveguides, optical switches, masks for plating, etching masks, color test systems, fiberglass cable coatings, stencils for screen printing, made by stereolithography Materials for three-dimensional objects, hologram recording materials, image recording materials, fine electronic circuits, decoloring materials, decoloring materials for image recording materials, decoloring materials for image recording materials using microcapsules, and light for printed wiring boards Resistant materials, photoresist materials for UV and visible laser direct image systems, photoresist materials and protective films used in the formation of dielectric layers in successive laminations of printed circuit boards, etc., but not special Limited to this use, it is particularly suitable for use in a display device for the above-mentioned use.

The display device of the present invention has the same structure as the conventionally known display device except that it has the hardened material (especially BCS) of the present invention. The BCS is preferably provided between the units.

When the polymerizable composition of the present invention is used as the black partition wall of the organic EL, it is preferable to use a weight average molecular weight of 5,000 or more in consideration of the verticalization of the pattern shape, the improvement of the development adhesion, and the improvement of the heat resistance. The alkaline developable compound is more preferably an alkaline developable compound having a weight average molecular weight of 7,000 to 15,000. Furthermore, it is particularly preferable when the basic developable compound is an unsaturated compound having a structure obtained by an esterification reaction, and the above-mentioned esterification reaction is included in the epoxy compound represented by the following general formula (IV) Esterification reaction of an epoxy addition compound having an unsaturated monobasic acid structure and a polybasic acid anhydride.

The method of manufacturing a hardened | cured material using the polymerizable composition of this invention, the photosensitive composition for BM, and the photosensitive composition for BCS is demonstrated in detail below.

The polymerizable composition, the photosensitive composition for BM, and the photosensitive composition for BCS of the present invention can be applied by a spin coater, a roll coater, a bar coater, a die coater, and a curtain type. Coating machines, various printing, and dipping methods are applied to support substrates such as soda glass, quartz glass, semiconductor substrates, metals, paper, and plastics. In addition, after being temporarily applied to a supporting substrate such as a film, it can also be transferred to another supporting substrate, and its application method is not limited.

In addition, as the light source of the energy ray used when curing the polymerizable composition and the photosensitive composition for BCS of the present invention, an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a mercury vapor 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. High-energy rays such as electron beams, X-rays, and radiation are preferably ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, xenon arc lamps, etc. that emit light having a wavelength of 300 to 450 nm.

Furthermore, because laser light is used for the exposure light source, a direct laser writing method that forms a direct image from digital information such as a computer without using a mask can not only improve productivity, but also achieve resolution or position accuracy. The laser light is useful because the laser light can be suitably used at a wavelength of 340 to 430 nm. Excimer lasers, nitrogen lasers, argon ion lasers, helium-cadmium lasers, helium-neon lasers, Samarium ion lasers, various semiconductor lasers, and YAG lasers emit light from the visible to the infrared region. In the case of using such lasers, a sensitizing pigment that absorbs the region from visible to infrared may be added.

The hardened | cured material of this invention is especially useful as BCS. BCS can be preferably formed by the following steps: (1) a step of forming a coating film of the photosensitive composition for BCS of the present invention on a substrate, and (2) irradiating the coating film through a mask having a specific pattern shape The step of radiating, (3) the step of baking after exposure, (4) the step of developing the film after exposure, and (5) the step of heating the film after development. As the mask, a multi-step mask such as a halftone mask or a grayscale mask may be used. [Example]

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

[Manufacturing Example 1] Preparation of lactam black dispersion B-1 An organic black pigment (Black 582 as lindamine black; manufactured by BASF), a dispersant (BYK-167), and a dispersion for dispersion A polymer (an alkali-developing compound PGMEA solution C-2 described later) was respectively mixed with 16 parts by mass, 3.2 parts by mass, and 3.6 parts by mass, and propylene glycol monomethyl ether was weighed so that the solid content concentration became 25% by mass. Acetate (PGMEA) was added to the mixture to make a mixture. After the above mixture was pre-mixed by a stirrer, zirconia beads with a diameter of 0.3 mm were added at the same weight as the dispersion (when the solvent PGMEA was removed from the mixture), and it was carried out at a temperature of 25 to 60 ° C. for 6 hours. The dispersion was treated with a paint shaker, and then zirconia beads were removed using a filter to obtain a dispersion. PGMEA was added to the obtained dispersion liquid, adjusted so that the dispersion concentration became 20% by mass, and homogenized by a stirrer to obtain a lactam black dispersion B-1.

[Manufacturing Example 2] Preparation of black dispersion B-2 An organic black pigment [CI Pigment Black 31 (Paliogen Black S 0084; manufactured by BASF)], a dispersant (BYK-167), and After dispersing the polymer (the basic developable compound PGMEA solution C-2 described later) at 12 parts by mass, 3.6 parts by mass, and 8 parts by mass, respectively, the weight was measured so that the solid content concentration became 25% by mass. Propylene glycol monomethyl ether acetate (PGMEA) was added to the mixture to prepare a mixture. After the above mixture was pre-mixed by a stirrer, zirconia beads with a diameter of 0.3 mm were added at the same weight as the dispersion (when the solvent PGMEA was removed from the mixture), and it was carried out at a temperature of 25 to 60 ° C. for 6 hours. The dispersion was treated with a paint shaker, and then zirconia beads were removed using a filter to obtain a dispersion. PGMEA was added to the obtained dispersion, and the dispersion was adjusted so that the concentration of the dispersion became 20% by mass. After homogenizing with a stirrer, a black dispersion B-2 was obtained.

[Production Example 3] Preparation of Carbon Black Dispersion Liquid B-3 20 parts by mass of MA100 (manufactured by Mitsubishi Chemical Corporation) as carbon black and 12.5 parts by mass of BYK161 (manufactured by BYK-Chemie (BYK)) as a dispersant (solid form The component concentration was 40% by mass), 67.5 parts by mass of propylene glycol monomethyl ether acetate was mixed as a solvent, and the mixture was processed by a bead mill to prepare a carbon black dispersion B-3.

[Manufacturing Example 4] Preparation of alkaline developable compound PGMEA solution C-2 Charged 1,1-bis [4- (2,3-glycidoxy) phenyl] indane 184 g, acrylic acid 58 g, 0.26 g of 2,6-di-third-butyl-p-cresol, 0.11 g of tetra-n-butylammonium bromide, and 105 g of PGMEA were stirred at 120 ° C for 16 hours. The reaction liquid was cooled to room temperature, 160 g of PGMEA, 59 g of biphenyltetracarboxylic dianhydride, and 0.24 g of tetra-n-butylammonium bromide were added, and stirred at 120 ° C for 4 hours. Further, 20 g of tetrahydrophthalic anhydride was added, and the mixture was stirred at 120 ° C for 4 hours, at 100 ° C for 3 hours, at 80 ° C for 4 hours, at 60 ° C for 6 hours, and at 40 ° C. After 11 hours, 128 g of PGMEA was added to obtain an alkaline developable compound C-2 (Mw = 5000, Mn = 2100, and acid value (solid content) of 92.7 mgKOH / g) as a PGMEA solution. The content of the alkali developable compound in the alkali developable compound PGMEA solution C-2 was 45% by mass.

[Production Example 5] Production of alkaline developable compound PGMEA solution C-3 Charge 9,9-bis (4-glycidyloxyphenyl) 茀 75.0 g, acrylic acid 23.8 g, 2,6-di-third 0.273 g of butyl-p-cresol, 0.585 g of tetrabutylammonium chloride, and 65.9 g of PGMEA, stirred at 90 ° C for 1 hour, stirred at 100 ° C for 1 hour, stirred at 110 ° C for 1 hour, and 120 ° C Under stirring 14. After cooling to room temperature, 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride, and 1.37 g of PGMEA were added, and 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-third-butyl-p-cresol, and 1.50 g of PGMEA were added, and it stirred at 90 degreeC for 90 minutes After stirring at 120 ° C for 4 hours, 122.2 g of PGMEA was added to obtain an alkaline developing compound C-3 (Mw = 4190, Mn = 2170, acid value (solid content)) as a target in the form of a PGMEA solution. 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 was mixed according to the composition of [Table 1] to [Table 4] to obtain a polymerizable composition (Examples 1 to 12 and comparison Examples 1 to 5). The numerical values of the composition in the table indicate parts by mass. The symbols of the components in the table indicate the following components. A1-1 Compound No. A1-1 [Polymerization initiator belonging to (A1) component] A2-1 Compound No. A2-1 [Polymerization initiator belonging to (A2) component] A2-2 Compound No. A2- 8 [Polymerization initiator belonging to the (A2) component] A2-3 Compound No. A2-14 [Polymerization initiator belonging to the (A2) component] A3-1 IRGACURE907 (α-aminophenethyl which does not have a hydroxyl group) Ketone compound; manufactured by BASF) B-1 lactam black dispersion B-1 B-2 black dispersion B-2 B-3 carbon black dispersion B-3 C-1 CCR-1171H (general formula (II The solid content of the PGMEA solution represented by the basic developing compound is 69.5% by mass; manufactured by Nippon Kayaku Co., Ltd.) C-2 Basic developing compound PGMEA solution C-2 C-3 Basic developing compound PGMEA solution C -3 D-1 Kayarad DPHA (Ethylene unsaturated compound; manufactured by Nippon Kayaku Co., Ltd.) D-2 UA-306H (carbamate monomer, PETA + HDI) E-1 γ-glycidoxypropyltrimethoxy Silane (coupling agent) E-2 Karenz PE-1 (thiol compound; manufactured by Showa Denko Corporation) G-1 PGMEA G-2 3-methoxybutyl acetate G-3 dimethyl succinate

[Evaluation of hardened material obtained from polymerizable composition] With respect to the hardened materials obtained from the polymerizable compositions of Examples 1 to 14 and Comparative Examples 1 to 5, the elastic recovery ratio and light-shielding property (OD value) were performed in the following order. ), Evaluation of relative dielectric constant, liquid crystal contamination (VHR), and chemical resistance. The results are collectively described in [Table 1] to [Table 4].

(Elastic Response Rate) The polymerizable composition of Examples 1 to 14 and the comparative polymerizable composition of Comparative Examples 1 to 5 were applied to a glass substrate by spin coating (3 μm thickness, 300 rpm × 7 seconds), After drying, pre-baking was performed at 90 ° C for 100 seconds. After removing the solvent, exposure was performed at 100 mJ / cm ^{2 with a} high-pressure mercury lamp using a photomask, and development was performed using a 0.04% by mass KOH aqueous solution. It heated at 30 degreeC for 30 minutes, and patterned. A 20-μm portion of the obtained pattern was subjected to a load-unload test with a load of 40 mN using a dynamic micro hardness tester DUH-211 of Shimadzu Corporation. The elastic response rate (%) was calculated by the following calculation formula. Elastic response rate (%) = [(response distance / compression displacement) × 100] Hardened products with an elastic response rate (%) of 60% or more can be used as BCS, and elastic response rates (%) of a hardened product of 70% or more It can be preferably used as BCS, and a hardened product having an elastic response rate (%) 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 (300 rpm, 7 seconds) were spin-coated on a glass substrate and dried, and then dried at 90 ° C. Pre-bake for 100 seconds. After exposure using an ultra-high pressure mercury lamp as a light source, baking was performed at 230 ° C. for 30 minutes to prepare a cured product. The OD value of the obtained film was measured using a Macbeth transmission densitometer, and the OD value was divided by the film thickness after baking to calculate the OD value per unit film thickness. Hardened products with unit film thickness of OD value of 1.0 or more have high light-shielding properties, so they can be used as BCS. Hardened products with unit film thickness of OD values of 1.5 or more can be used as BCS. A hardened material having a value of 2.0 or more is particularly preferably used as BCS. Hardened products with an OD value of less than 1.0 per unit film thickness cannot be used as BCS.

(Relative permittivity) The polymerizable composition of Examples 1 to 14 and the comparative polymerizable composition of Comparative Examples 1 to 5 (3 μm thick, 300 rpm × 7 seconds) were spin-coated on a glass substrate and dried. Then, pre-baking was performed at 90 ° C for 100 seconds, and exposure was performed at 100 mJ / cm ² by a high-pressure mercury lamp without using a mask, followed by heating at 230 ° C for 180 minutes to prepare the above-mentioned evaluation sample. (Evaluation method) About the said evaluation sample, it measured using LCR meter, 4284A of Agilent, and applied AC1V and 1 kHz. Hardened products with a relative dielectric constant of less than 5.0 can be used as BCS, hardened products with a relative dielectric constant of 4.5 or less can be preferably used as BCS, and hardened products with a relative dielectric constant of 4.0 or less can be particularly used as BCS. Best to use. Hardened products having a relative dielectric constant of 5.0 or more cannot be used as BCS.

(VHR) The polymerizable composition obtained in Examples 1 to 14 and the comparative polymerizable composition obtained in Comparative Examples 1 to 5 were applied to a glass substrate (100 mm × 100 mm) using a spin coater, and Pre-baking was performed at 90 ° C for 100 seconds to form a coating film having a film thickness of 3.0 μm. Next, a specular projection alignment exposure device (product name: TME-150RTO, manufactured by Topcon Co., Ltd.) was used, and the coating film was irradiated with ultraviolet rays at an irradiation amount of 200 mJ / cm ² without a mask. Thereafter, it was baked at 230 ° C for 30 minutes. One part by mass of the post-bake coating film and 40 parts by mass of a liquid crystal "RS-182" manufactured by ADEKA Corporation were mixed and stored at 120 ° C for 1 hour. After taking it out and leaving it to stand at room temperature, the supernatant was collected. The VHR (voltage holding ratio) of the taken liquid crystal composition was measured. The detailed evaluation method is as follows. The liquid crystal composition was poured into a TN cell for liquid crystal evaluation (cell thickness: 5 μm, electrode area: 8 mm × 8 mm, alignment film: JALS2096), and VHR-1A (manufactured by Toyo Technology Co., Ltd.) was used to measure VHR. (Measurement conditions: Pulse voltage width is 60 μs, frame period is 16.7 ms, wave height is ± 5 V, and measurement temperature is 60 ° C.) Hardened materials with VHR of 90% or above have low liquid crystal contamination and can be used as BCS. A hardened product having a VHR of 95% or more can be preferably used as BCS, and a hardened product having a VHR of 98% or more can be particularly preferably used as BCS. Hardened products with VHR less than 90% cannot be used as BCS.

<NMP Chemical Resistance> The N-methylpyrrolidone (NMP) dissolution test was performed in the following procedure. First, the polymerizable composition obtained in Examples 1 to 14 and the comparative polymerizable composition obtained in Comparative Examples 1 to 5 were applied by a spin coater so that the final film thickness became 3 μm. The cloth was dried on a glass substrate for 1 minute under reduced pressure, and then dried on a hot plate at 90 ° C. for 120 seconds. After exposure to 50 mJ / cm ² by a high-pressure mercury lamp, and after a development step, heating was performed at 230 ° C. for 40 minutes in an oven to obtain a resist-coated substrate. Two substrates for measurement (25 mm × 35 mm square) were cut out of the prepared resist-coated substrate, and immersed in a 10 mL vial containing 8 mL of N-methylpyrrolidone (NMP). in. Next, the NMP dissolution test was performed while the vial with the substrate for measurement placed in a clean oven at 90 ° C. for 60 minutes. After standing for 40 minutes, the vial was taken out of the hot bath, and the NMP elution solution was measured by a spectrophotometer ("UV-3100PC" manufactured by Shimadzu Corporation) at a wavelength range of 300 to 800 nm every 1 nm. Absorbance. The light source was a halogen lamp and a deuterium lamp (the switching wavelength was 360 nm), the detector was a photomultiplier, and the slit width was 2 nm as the measurement condition. The sample solution was placed in a 1 cm square quartz cell for measurement. The absorbance is a dimensionless quantity that indicates how much the light intensity is attenuated when light passes through an object in a spectroscopic method, and is defined by the following formula.

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

In addition, the above-mentioned incident light intensity and transmitted light intensity can be regarded as the light intensity I ₀ that passes through the NMP alone and the light intensity I that passes through the sample solution when the sample light and the separate NMP are incident from the same light source. Therefore, (I / I ₀ ) in the above formula represents the light transmittance, and the absorbance A refers to a value in which the reciprocal of the transmittance is represented by a logarithm. The absorbance A is a notation used when calculating the concentration and the like of a substance contained in a sample solution. When the absorbance A = 0, it indicates a state where light is not absorbed at all (transmittance is 100%), and when the absorbance A = ∞, it indicates a state where light is not transmitted at all (transmittance 0%). That is, the stronger the absorbance, the more the component of the resist coating film is eluted into the NMP, and the NMP resistance is poor. The measured spectral area (nm) of the absorbance was calculated and evaluated based on the following criteria. NMP chemical resistance evaluation criteria: Determined based on the area value of the absorption spectrum of the NMP elution solution (wavelength 300 to 800 nm) ○: less than 20 (nm) △: more than 20 (nm) and less than 60 (nm) ×: 60 (nm) or more NMP chemical resistance evaluation can be used as BCS, especially better, NMP chemical resistance evaluation △ can be used as BCS, NMP chemical resistance evaluation is not possible Used as BCS. The spectral area of the absorbance used as the evaluation criterion can be expressed by the sum of the absorbances of the respective wavelengths, and represents the total of the eluted resist components.

[Table 1]

[Table 2]

[table 3]

[Table 4]

From [Table 1] to [Table 4], it can be seen that the hardened material obtained from the polymerizable composition of the present invention satisfies light-shielding property (OD value), relative dielectric constant, low liquid crystal contamination resistance (VHR), and Chemical properties and excellent elastic response make it useful as a BCS. [Industrial availability]

The hardened material obtained from the polymerizable composition, the photosensitive composition for BM or the photosensitive composition for BCS of the present invention is a hardened material having excellent elastic response, light-shielding properties, chemical resistance, low dielectric constant, and good electrical properties. Particularly suitable for BCS. This hardened | cured material is especially useful in a display device, etc.

Claims (9)

A polymerizable composition containing a polymerization initiator (A), a colorant (B), an alkaline developable compound (C), and an ethylenically unsaturated compound other than the alkaline developable compound (C) ( D) The polymerization initiator (A) contains an α-aminoacetophenone compound (A1) having a hydroxyl group. The polymerizable composition according to claim 1, wherein the polymerization initiator (A) contains, in addition to the α-aminoacetophenone compound (A1) having a hydroxyl group, a group having a group represented by the following general formula (I) Oxime ester compound (A2); (In the formula, 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 heterocyclic group containing 2 to 20 carbon atoms. The hydrogen atom in the group represented by R ¹ and R ² passes through a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amine group, a carboxyl group, a methacryl group, an acryl group, an epoxy group, a vinyl group, and a vinyl ether group. In the case of substitution with a mercapto group, an isocyanate group, or a group containing 2 to 20 carbon atoms containing a heterocyclic ring, and the methylene group in the group represented by R ¹ and R ² is substituted with -O-, -CO -, -COO-, -OCO-, -NR ^3- , -NR ³ CO-, -S-, -CS-, -SO _2- , -SCO-, -COS-, -OCS-, unsaturated bond or In the case of CSO-, R ³ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, m represents 0 or 1, and * in the formula represents a bonding bond). The polymerizable composition according to claim 1, wherein the colorant (B) is a black pigment. The polymerizable composition according to claim 1, wherein the alkaline developable compound (C) is an alkaline developable compound represented by the following general formula (II); (In the formula, 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 carbon atom containing a heterocyclic ring. The base is a number of 2 to 20. When there are a plurality of cases of R ¹³ and R ¹⁴ , the same situation exists and there are different situations. Y ¹ , Y ^2, and Y ³ represent direct bonds, and the number of carbon atoms is 1 to 20. In the case of a hydrocarbon group or a heterocyclic-containing carbon group having 2 to 20 carbon atoms, when there are a plurality of Y ² , there are the same situations and different situations. Z ¹ , Z ² and Z ³ represent the number of carbon atoms as In the case of a hydrocarbon group of 1 to 20 or a group of 2 to 20 carbon atoms containing a heterocyclic ring, when there are a plurality of Z ² , there are the same cases and different cases. There are R ¹² , R ¹⁴ , R ¹⁶ , The hydrogen atom in the group represented by Y ¹ , Y ² , Y ³ , Z ¹ , Z ² and Z ³ passes a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amine group, a carboxyl group, a methacryl group, and acryl group. In the case of the substitution of an alkyl group, an epoxy group, a vinyl group, a mercapto group, an isocyanate group or a group containing 2 to 20 carbon atoms containing a heterocyclic ring, and there are also R ¹² , R ¹⁴ , R ^16, Y ^1, Y ^2, the group represented by Y ^3, Z ^1, Z ² and Z ³ in the methylene group is replaced by -O -, - CO -, - COO -, - OCO -, - S- , -SO _2- , -SCO- or -COS-, n is a positive number below 0 or 10, a is a positive number below 0 or 4, b is a positive number below 0 or 3, and c is a number below 0 or 4 A positive number, when n is 2 or more, b is the same or different.) The photosensitive composition for black matrices containing the polymerizable composition as described in any one of Claims 1-4. A photosensitive composition for a black column spacer, comprising the polymerizable composition according to any one of claims 1 to 4. A method for producing a cured product, which comprises producing a cured product by irradiating or heating the polymerizable composition according to any one of claims 1 to 4. A hardened | cured material is a hardened | cured material of the polymerizable composition as described in any one of Claims 1-4. A display display device containing the hardened material as claimed in claim 8.