KR20180136899A - Resin Composition, Cured Film, Color Filter, and Preparing Method of Cured Film - Google Patents

Abstract

The present invention provides a resin composition which can form a pattern which has good adhesion and can inhibit occurrence of development residue in a non-exposure unit, a manufacturing method of a cured film which utilizes the resin composition, a cured film which is formed by curing the resin composition, and a color filter which provides the cured film. A compound which is represented by a following formula (e1) as silane coupling agent (E) is mixed with a resin compound which includes an alkali soluble resin (A), a photopolymeric compound (B), a photopolymerization initiator (C) and a pigment (D). (e1): (R^(e1)O_()a)(R^(e2))_(3-a)Si-R^(e3)-NH-CO-R^(e4)-R^(e5) (in formula (e1), R^(e1) and R^(e2) is a hydrocarbon group which independently has the atom number of carbon of 1-6, a is 2 or 3, R^(e3) is an alkylene group which has the atom number of carbon of 1-10, R^(e4) is a divalent organic group, and R^(e5) is a Brønsted acidic group, an alcoholic hydroxyl group, an amino group, or a carbamoyl group.)

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, a cured film, a color filter,

The present invention relates to a resin composition, a cured film formed by curing the resin composition, a color filter comprising the cured film, and a method for producing a cured film using the resin composition.

A display body such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates on which pairs of electrodes are formed facing each other. A color filter having pixels of respective colors of red (R), green (G), and blue (B) is formed on the inner side of one substrate. In this color filter, in order to prevent mixed colors of different colors in each pixel or to hide the patterns of the electrodes, a black matrix arranged in a matrix form is usually formed so as to divide pixels of R, G and B colors .

Generally, a color filter is formed by a lithography method. Specifically, first, a black photosensitive composition is coated on a substrate, exposed and developed to form a black matrix. Thereafter, coating, exposure and development are repeated for each of the red (R), green (G) and blue (B) photosensitive compositions to form respective color patterns at predetermined positions to form a color filter .

As a method of forming a coloring film constituting a color filter, for example, a method of forming a black matrix, a method using a negative-type photosensitive resin composition has been proposed.

For example, Patent Document 1 discloses a black photosensitive resin composition which is a raw material of a black matrix capable of achieving both high-order light properties and low reflectance at low cost, and a negative-type photosensitive resin composition comprising carbon black and hydrophobic silica fine particles Lt; / RTI >

Japanese Patent Laid-Open Publication No. 2015-161815

However, the inventors of the present invention have found that when a conventional photosensitive resin composition such as the composition described in Patent Document 1 is used, it is difficult to form a pattern closely adhering to the substrate, or a residue tends to occur in the unexposed portion I learned that there is an assignment.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a resin composition capable of forming a pattern having good adhesion to a substrate and suppressing the generation of development residue in the unexposed portion, A cured film formed by curing the resin composition, and a color filter including the cured film.

The inventors of the present invention have found that when a compound having a specific structure described below is added to a resin composition containing an alkali soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a pigment (D) And the present invention has been accomplished based on these findings. Specifically, the present invention provides the following.

According to a first aspect of the present invention,

The alkali-soluble resin (A)

The photopolymerizable compound (B)

A photopolymerization initiator (C)

The pigment (D)

Silane coupling agent (E)

, Wherein the resin composition

Wherein the silane coupling agent (E) is represented by the following formula (e1):

(R ^e1 ) _a (R ^e2 ) _3-a Si-R ^e3 -NH-CO-R ^e4 -R ^e5 (e1)

(In the formula (e1), R ^e1 and R ^e2 are A is 2 or 3, R ^e3 is an alkylene group having 1 to 10 carbon atoms, R ^e4 is a divalent organic group, and R ^e5 is a hydrocarbon group having 1 to 6 carbon atoms, An acidic group, an alcoholic hydroxyl group, an amino group, or a carbamoyl group.

Is an alkoxysilane compound represented by the following general formula (1).

A second aspect of the present invention is a cured film obtained by curing a resin composition related to the first aspect.

A third aspect of the present invention is a color filter having a cured film related to the second aspect.

A fourth aspect of the present invention is a method for manufacturing a semiconductor device comprising the steps of forming a coating film by applying a resin composition related to the first aspect,

A step of positionally selectively exposing the coating film,

A step of developing the exposed coated film to form a patterned cured film,

And a step of baking the patterned cured film.

According to the present invention, there is provided a resin composition capable of forming a pattern having good adhesion to a substrate and suppressing the occurrence of development residue in the unexposed portion, a process for producing a cured film using the resin composition, And a color filter including the cured film can be provided.

Hereinafter, the present invention will be described based on a preferred embodiment. In the present specification, " ~ " indicates the following (upper limit) from the ideal (lower limit) unless otherwise noted.

≪ Resin composition &

The resin composition comprises an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a pigment (D) and a silane coupling agent (E).

The silane coupling agent (E) is represented by the following formula (e1):

(R ^e1 ) _a (R ^e2 ) _3-a Si-R ^e3 -NH-CO-R ^e4 -R ^e5 (e1)

(In the formula (e1), R ^e1 and R ^e2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, a is 2 or 3, R ^e3 is an alkylene group having 1 to 10 carbon atoms, R ^e4 Is a bivalent organic group and R ^e5 is a Bronsted acid group, an alcoholic hydroxyl group, an amino group, or a carbamoyl group.)

Lt; / RTI >

In the present embodiment, the resin composition includes the above-mentioned silane coupling agent (E), whereby a resin composition capable of forming a pattern with good adhesion to the substrate and suppressing the occurrence of development residue in the unexposed portion .

Hereinafter, essential or optional components contained in the resin composition and a method for preparing the resin composition will be described.

≪ Alkali-soluble resin (A) >

The resin composition includes an alkali-soluble resin (A) (also referred to as " component (A) " in this specification). The alkali-soluble resin (A) is not particularly limited and may be appropriately selected from alkali-soluble resins conventionally blended with various photosensitive resin compositions.

Here, in the present specification, the alkali-soluble resin (A) refers to a resin having a functional group (for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, etc.)

A resin suitable as an alkali-soluble resin includes a resin (A1) having a cardo structure (hereinafter also referred to as " cardo resin (A1) ").

When a resin having a cardo structure (A1) is used as an alkali-soluble resin, it is easy to obtain a resin composition having excellent resolution and a resin composition can easily form a cured film which is difficult to flow excessively by heating.

[Resin (A1) having a cardo structure]

As the resin (A1) having a cardo structure, a resin having a cardo framework in its structure and having a predetermined alkali solubility can be used. The cardo skeleton refers to a skeleton in which a second cyclic structure and a third cyclic structure are bonded to one ring carbon atom constituting the first cyclic structure. The second annular structure and the third annular structure may have the same structure or different structures.

A typical example of the cardo skeleton is a skeleton in which two aromatic rings (for example, a benzene ring) are bonded to the carbon atom at the 9-position of the fluorene ring.

The (A1) cardo structure resin is not particularly limited, and conventionally known resins can be used. Among them, a resin represented by the following formula (a-1) is preferable.

However,

In the formula (a-1), X ^a represents a group represented by the following formula (a-2). m1 represents an integer of 0 to 20;

[Figure 2]

The formula (a2) of, R ^a1 are each independently a hydrocarbon group, or a halogen atom, a hydrogen atom, the carbon atom 1 ~ 6, R ^a2 are each independently a hydrogen atom or a methyl group, R ^a3 is Independently represents a linear or branched alkylene group, m2 represents 0 or 1, and W ^a represents a group represented by the following formula (a-3).

[Figure 3]

In formula (a-2), R ^a3 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, particularly preferably an alkylene group having 1 to 6 carbon atoms Most preferably an ethane-1,2-diyl group, a propane-1,2-diyl group, and a propane-1,3-diyl group.

Ring A in the formula (a-3) represents an aliphatic ring which may be condensed with an aromatic ring or may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocycle.

Examples of the aliphatic ring include monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane.

Specific examples thereof include monocycloalkane such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and adamantane, norbornane, isoborane, tricyclodecane, and tetracyclododecane.

The aromatic ring to be condensed in the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle, and an aromatic hydrocarbon ring is preferable. Specifically, a benzene ring and a naphthalene ring are preferable.

Suitable examples of divalent groups represented by formula (a-3) include the following groups.

[Figure 4]

The divalent X ^a in the formula (a-1) is introduced into the (A1) cardoy resin by reacting the tetracarboxylic dianhydride giving the residue Z ^a and the diol compound represented by the following formula (a-2a).

[Figure 5]

In formula (a-2a), R ^a1 , R ^a2 , R ^a3 , and m2 are as described for formula (a-2). The ring A in the formula (a-2a) is as described for the formula (a-3).

The diol compound represented by the formula (a-2a) can be produced, for example, by the following method.

First, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) is replaced with a group represented by -R ^a3 -OH according to the conventional method, and then epichlorohydrin or the like is added thereto To obtain an epoxy compound represented by the following formula (a-2c).

Next, the diol compound represented by the formula (a-2a) is obtained by reacting the epoxy compound represented by the formula (a-2c) with acrylic acid or methacrylic acid.

In formula (a-2b) and formula (a-2c), R ^a1 , R ^a3 , and m2 are as described for formula (a-2). The ring A in the formula (a-2b) and the formula (a-2c) is as described for the formula (a-3).

The method for producing the diol compound represented by the formula (a-2a) is not limited to the above method.

[6]

Suitable examples of the diol compound represented by the formula (a-2b) include the following diol compounds.

[Figure 7]

In the above formula (a-1), R ^a0 is a hydrogen atom or a group represented by -CO-Y ^a -COOH. Here, Y ^a represents a residue other than an acid anhydride group (-CO-O-CO-) from ^a dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-undo-methylene tetrahydrophthalic acid, anhydrous chlorodic acid, methyltetrahydrophthalic anhydride, And anhydrous glutaric acid.

In the above formula (a-1), Z ^a represents a residue other than the two acid anhydride groups from the tetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like represented by the following formula (a-4) .

In the above formula (a-1), m represents an integer of 0 to 20.

[Figure 8]

(In the formula (a-4), R ^a4 , R ^a5 and R ^a6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, Represents an integer of 12.)

The alkyl group which may be selected as R ^a4 in the formula (a-4) is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms contained in the alkyl group within this range, the heat resistance of the obtained carboxylic acid ester can be further improved. When R ^a4 is an alkyl group, the number of carbon atoms thereof is preferably from 1 to 6, more preferably from 1 to 5, still more preferably from 1 to 4, and still more preferably from 1 to 3, from the viewpoint of obtaining a carboxyl resin having excellent heat resistance. Is particularly preferable.

When R ^a4 is an alkyl group, the alkyl group may be linear or branched.

As R ^a4 in the formula (a-4), a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is more preferable, independently from each other, since it is easy to obtain a carboxy resin having excellent heat resistance. R ^a4 in the formula (a-4) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group.

It is preferable that a plurality of R ^a4 in the formula (a-4) is the same group because the preparation of the high purity tetracarboxylic acid dianhydride is easy.

M3 in the formula (a-4) represents an integer of 0 to 12; By setting the value of m3 to 12 or less, purification of the tetracarboxylic dianhydride can be facilitated.

From the viewpoint of easy purification of the tetracarboxylic acid dianhydride, the upper limit of m3 is preferably 5, more preferably 3.

From the viewpoint of the chemical stability of the tetracarboxylic acid dianhydride, the lower limit of m3 is preferably 1, more preferably 2.

M3 in the formula (a-4) is particularly preferably 2 or 3.

The alkyl group having 1 to 10 carbon atoms which may be selected as R ^a5 and R ^a6 in the formula (a-4) is the same as the alkyl group having 1 to 10 carbon atoms which can be selected as R ^a4 .

R ^a5 and R ^a6 are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 carbon atom, in view of easy purification of tetracarboxylic dianhydride. To 4, particularly preferably 1 to 3) alkyl groups, and particularly preferably a hydrogen atom or a methyl group.

Examples of the tetracarboxylic dianhydride represented by the formula (a-4) include norbornane-2-spiro-a-cyclopentanone-a'-spiro-2 " -norbornane- , 6,6 "-tetracarboxylic dianhydride (also known as" norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-norbornane- 6 "-tetracarboxylic dianhydride"), methyl norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''- (methylnorbornane) -5,5 " 6 "-tetracarboxylic dianhydride, norbornane-2-spiro-a-cyclohexanone-a'-spiro-2" -norbornane-5,5 " 2 ' -norbornane-5,5 ", 6,6 " -tetracarboxylic dianhydride " Spiro-? -Cyclohexanone-? '- spiro-2' '- (methylnorbornane) -5,5' ', 6,6 "-tetracarboxylic dianhydride, Norbornane-2-spiro- [alpha] -cyclopropanone-alpha ' -spiro -2''-norbornane-5,5 '', 6,6'-tetracarboxylic dianhydride, norbornane-2-spiro-a-cyclobutanone-a'-spiro- Borane-5,5 ", 6,6 " -tetracarboxylic dianhydride, norbornane-2-spiro- alpha -cycloheptanone- '', 6,6 '' -tetracarboxylic dianhydride, norbornane-2-spiro-a-cyclooctanone-a'-spiro-2''-norbornane-5,5 ' -'-tetracarboxylic acid dianhydride, norbornane-2-spiro-a-cyclononanone-a'-spiro-2''-norbornane-5,5 '', 6,6'-tetracarboxylic acid 2 Spiro-α-cyclodecanone-α'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic dianhydride, norbornane- Spiro-a-cyclodecanone-a'-spiro-2''-norbornane-5,5 '', 6,6'-tetracarboxylic dianhydride, norbornane- Cyclododecanone-a'-spiro-2 " -norbornane-5,5 ", 6,6 " -tetracarboxylic acid 2 Norbornane-2-spiro- alpha -cyclotridecanone-alpha'-spiro-2''-norbornane-5,5 '', 6,6'-tetracarboxylic dianhydride, norbornane Spiro-a-cyclotetradecanone-a'-spiro-2''-norbornane-5,5 '', 6,6'-tetracarboxylic dianhydride, norbornane- -cyclopentadecanol-a'-spiro-2''-norbornane-5,5 '', 6,6 "-tetracarboxylic dianhydride, norbornane-2-spiro- Pentane) -α'-spiro-2''-norbornane-5,5 '', 6,6 "-tetracarboxylic dianhydride, norbornane-2-spiro-α- (methylcyclohexanone) -α'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic dianhydride, and the like.

The weight average molecular weight of the (A1) cardo resin is preferably 1,000 to 40,000, more preferably 1,500 to 30,000, and still more preferably 2,000 to 10,000. Within the above range, sufficient heat resistance and film strength can be obtained while satisfactory developability is obtained.

[Acrylic resin (A2)]

The alkali-soluble resin (A) may contain an alkali-soluble resin other than the cardo resin (A1). As such an alkali-soluble resin, an acrylic resin (A2) can be mentioned.

As the acrylic resin (A2), those containing a constituent unit derived from (meth) acrylic acid and / or a constituent unit derived from another monomer such as (meth) acrylate can be used. (Meth) acrylic acid is acrylic acid, or methacrylic acid. (Meth) acrylic acid ester is represented by the following formula (a-5), and is not particularly limited so long as it does not impair the purpose of the present invention.

[Figure 9]

In the formula (a-5), R ^a7 is a hydrogen atom or a methyl group, and R ^a8 is a monovalent organic group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic.

Substituents other than the hydrocarbon group in the organic group of R ^a8 are not particularly limited as long as the effect of the present invention is not impaired and examples thereof include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyanato groups, A silyl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxyl group, a carboxylate group, a cyano group, A sulfonyl group, a sulfonyl group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, a hydroxyimino group, an alkyl ether group, an alkylthioether group, an aryl ether An amino group (-NH ₂ , -NHR, -NRR ': where R and R' each independently represents a hydrocarbon group), and the like. The hydrogen atom contained in the substituent may be substituted by a hydrocarbon group. The hydrocarbon group contained in the substituent may be any of straight chain, branched chain and cyclic.

R ^a8 is preferably an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, and these groups may be substituted with a halogen atom, a hydroxyl group, an alkyl group or a heterocyclic group. When these groups include an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.

When the alkyl group is straight chain or branched chain, the number of carbon atoms is preferably from 1 to 20, more preferably from 1 to 15, and particularly preferably from 1 to 10. Examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-hexyl group, n-heptyl group, n-octyl group, isooxyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, And the like.

When the alkyl group is a group containing an alicyclic group or an alicyclic group, examples of suitable alicyclic groups contained in the alkyl group include monocyclic alicyclic groups such as cyclopentyl group and cyclohexyl group, alicyclic groups such as adamantyl group, norbornyl group, isobonyl group, A tricyclodecyl group, and a tetracyclododecyl group, and the like can be given.

The acrylic resin (A2) may be obtained by polymerizing monomers other than the (meth) acrylic acid ester. Examples of such a monomer include (meth) acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters and styrenes. These monomers may be used alone or in combination of two or more.

Examples of the (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, Acrylamide, N-methyl-N-phenyl (meth) acrylamide and N-hydroxyethyl-N-methyl (meth) acrylamide.

Examples of the unsaturated carboxylic acids include monocarboxylic acids such as crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Anhydrides of these dicarboxylic acids; And the like.

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; Allyloxyethanol; And the like.

Examples of the vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether , 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, and tetrahydrofurfuryl vinyl ether Alkyl vinyl ethers; Vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl anthranyl ether; And the like.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethylacetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, Acetate, vinyl acetoacetate, vinyl lactate, vinyl-beta-phenylbutylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthoate.

Examples of the styrenes include styrene; Examples of the monomer include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, , And acetoxymethylstyrene; Alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; But are not limited to, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo- Styrene, and 4-fluoro-3-trifluoromethylstyrene; And the like.

The amount of the constituent unit derived from (meth) acrylic acid and the amount of the constituent unit derived from the other monomer in the acrylic resin (A2) is not particularly limited within the range not hindering the object of the present invention. The amount of the structural unit derived from (meth) acrylic acid in the acrylic resin (A2) is preferably from 5 to 50 mass%, more preferably from 10 to 30 mass%, based on the mass of the acrylic resin.

The weight average molecular weight of the acrylic resin (A2) is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000. Within the above range, there is a tendency that the film forming ability of the resin composition and the balance of developability after exposure tends to be easily obtained.

[Novolak resin (A3)]

It is also preferable that the alkali-soluble resin contains a novolak resin (A3) from the viewpoint of suppressing excessive heat flow of the cured film due to heating during post-baking.

As the novolak resin (A3), various novolac resins conventionally blended with a photosensitive resin composition can be used. The novolac resin (A3) is preferably obtained by subjecting an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenol") and an aldehyde to an addition condensation under an acid catalyst.

(Phenols)

Examples of the phenol used in the production of the novolak resin (A3) include phenol; cresols such as o-cresol, m-cresol and p-cresol; Such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5- Sileenol; ethyl phenols such as o-ethyl phenol, m-ethyl phenol and p-ethyl phenol; Alkylphenols such as 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol and p-tert-butylphenol; Trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; Polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and fluoroglycinol; Alkylpolyphenols such as alkyl resorcin, alkyl catechol and alkyl hydroquinone (all alkyl groups having 1 to 4 carbon atoms); alpha -naphthol; ? -naphthol; Hydroxydiphenyl; And bisphenol A. These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. In this case, various properties such as heat resistance of the cured film formed using the resin composition can be controlled by adjusting the blending ratio of both.

The mixing ratio of m-cresol and p-cresol is not particularly limited, but is preferably 3/7 to 8/2 by mole in terms of the molar ratio of m-cresol / p-cresol. By using m-cresol and p-cresol in this range, it is easy to obtain a resin composition capable of forming a cured film having excellent heat resistance.

A novolak resin prepared by using m-cresol in combination with 2,3,5-trimethylphenol is also preferable. When such a novolac resin is used, a resin composition capable of forming a cured film which is difficult to flow excessively by heating during post-baking is particularly easy to obtain.

The blending ratio of m-cresol to 2,3,5-trimethylphenol is not particularly limited, but it is preferably 70/30 to 95/5 in molar ratio of m-cresol / 2,3,5-trimethylphenol.

(Aldehydes)

Examples of the aldehyde used in the production of the novolak resin (A3) include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone, or two or more aldehydes may be used in combination.

(Acid catalyst)

Examples of the acid catalyst used for producing the novolak resin (A3) include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; Organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfuric acid, and para-toluenesulfonic acid; And metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

(Molecular Weight)

The weight average molecular weight (Mw) of the novolak resin (A3) in terms of polystyrene (hereinafter simply referred to as "weight average molecular weight") is preferably from the lower limit value Preferably 2000, more preferably 5000, particularly preferably 10000, more preferably 15000, most preferably 20,000, and the upper limit is preferably 50000, more preferably 45000, still more preferably 40000, and still more preferably 35000 Is most preferable.

As the novolac resin (A3), at least two kinds of the novolak resins (A3) having different weight average molecular weights in terms of polystyrene may be used in combination. A balance between the developability of the resin composition and the heat resistance of the cured film formed using the resin composition can be achieved by using a combination of large and small ones having different weight average molecular weights.

The content of the alkali-soluble resin (A) is preferably 10 to 65% by mass, and more preferably 15 to 50% by mass with respect to the mass of the entire solid content of the resin composition. Within the above range, it is easy to obtain a resin composition having excellent developing properties.

When the cardo resin (A1) is used, its content is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and more preferably 15 to 30% by mass with respect to the mass of the entire solid content of the resin composition More preferable. By setting the thickness within the above range, it is possible to form a cured film which is difficult to flow excessively by heating at the time of post-baking, and it is easy to obtain a resin composition excellent in developing property.

When the acrylic resin (A2) is used, the content thereof is preferably 2 to 55 mass%, more preferably 4 to 50 mass%, and more preferably 8 to 45 mass% with respect to the mass of the total solid content of the resin composition desirable. By setting the thickness within the above range, it is possible to form a cured film which is difficult to flow excessively by heating at the time of post-baking, and a resin composition excellent in developability can be easily obtained.

When the novolak resin (A3) is used, the content thereof is preferably 0.2 to 15 mass%, more preferably 0.5 to 10 mass%, and more preferably 0.8 to 5 mass% with respect to the mass of the entire solid content of the resin composition More preferable. By setting the thickness within the above range, it is possible to form a cured film which is difficult to flow excessively by heating at the time of post-baking, and a resin composition excellent in developability can be easily obtained.

≪ Photopolymerizable compound (B) >

The resin composition comprises a photopolymerizable compound (B). As the photopolymerizable compound (B), a monomer having an ethylenic unsaturated group is preferable. These monomers include monofunctional monomers and polyfunctional monomers.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (Meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic anhydride, itaconic acid, (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, tert-butyl acrylamide sulfonic acid, Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate (Meth) acrylate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half . These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di Acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, diethylene glycol di (meth) acrylate, (Meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol (Meth) acrylates such as hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane, (Meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate, trimethylhexamethylene diisocyanate, or hexamethylene di (Condensation product of polyhydric alcohol and N-methylol (meth) acrylamide), methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, And the like, or monomers, acrylic tree formal. These polyfunctional monomers may be used alone or in combination of two or more.

Of these monomers having an ethylenically unsaturated group, polyfunctional monomers having three or more functional groups are preferred, and polyfunctional monomers having four or more functional groups are more preferable because of the tendency to increase the adhesion of the resin composition to the substrate and the strength of the resin composition after curing. And a polyfunctional monomer having five or more functionalities is more preferable.

Specifically, it is preferable to use a polyfunctional monomer having five or more functionalities, and it is more preferable to use dipentaerythritol penta (meth) acrylate and / or dipentaerythritol hexa (meth) acrylate.

The content of the photopolymerizable compound (B) in the resin composition is preferably 1 to 50 mass%, more preferably 5 to 40 mass%, with respect to the mass of the total solid content of the resin composition. When the content is in the above range, there is a tendency to balance the sensitivity, developability and resolution.

≪ Photopolymerization initiator (C) >

The photopolymerization initiator (C) is not particularly limited, and conventionally known photopolymerization initiators can be used.

Specific examples of the photopolymerization initiator (C) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl 2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, O (9-ethyl-6-nitro-9H-carbazol-3-yl) -acetyl-1- [6- (2-methylbenzoyl) -9- 1- [4- (2-methoxy-1-methylethoxy) -2-methylphenyl] methanone O-acetyl oxime, 2- (benzoyloxyimino) Trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimetyl Methylbenzoic acid, methyl benzoate, methyl benzoate, ethyl benzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, Dimethyl ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4- , 4-dimethylthioxanthone, 1-chloro-4-propoxycitoxone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2- Benzoyl peroxide, cumene hydroperoxide, cumene hydroperoxide, isobutyl peroxide, isobutyl peroxide, isopropyl thioxanthene, 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl 2 Benzophenone, 2-chlorobenzophenone, p, p'-bisdimethyl Benzophenone, benzoin phenol, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, Ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, Propylphenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, .alpha., .Alpha.-butyrolactophenone, dichloroacetophenone, trichloroacetophenone, -Dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxy tri Azine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) 2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (trichloromethyl) -s-triazine, 2- [2- (3, 4-diethylamino-2-methylphenyl) (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4- 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2, 4-Bis-trichloromethyl-6- (2-bromo 4-methoxy) styryl phenyl -s- triazine, and the like. These photopolymerization initiators may be used alone or in combination of two or more.

Among them, it is particularly preferable to use an oxime-type photopolymerization initiator in terms of sensitivity. Among the oxime-based photopolymerization initiators, particularly preferred are O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol- (O-acetyloxime), and 2- (benzoyloxyimino) -1- [4- ( Phenylthio) phenyl] -1-octanone.

As the photopolymerization initiator, it is also preferable to use a oxime-based compound represented by the following formula (c1).

[10]

(R ^c1 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group,

n1 is an integer of 0 to 4,

n2 is 0 or 1,

R ^c2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent,

R ^c3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

In the formula (c1), R ^c1 is not particularly limited within the range that does not impair the object of the present invention, and is appropriately selected from various organic groups. Suitable examples of R ^{c1 in the} case where R ^c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, a phenyl group which may have a substituent, A phenoxycarbonyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group , A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, An amino group substituted by an organic group of 1 or 2, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen, a nitro group, And the like. When n1 is an integer of 2 to 4, ^Rc1 may be the same or different. The number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent further having a substituent.

When R ^c1 is an alkyl group, the number of carbon atoms is preferably from 1 to 20, and more preferably from 1 to 6 carbon atoms. When R ^c1 is an alkyl group, it may be a linear chain or a branched chain. Specific examples of the R ^c1 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- n-hexyl group, n-heptyl group, n-octyl group, iso-octyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n- And an isodecyl group. When R ^c1 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c1 is an alkoxy group, the number of carbon atoms is preferably from 1 to 20, and more preferably from 1 to 6 carbon atoms. When R ^c1 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of when R ^c1 is an alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec- N-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, isohexyloxy group, isopentyloxy group, sec- tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ^c1 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propoxyoxyethoxyethoxy group, and a methoxy Propyloxy group and the like.

When R ^c1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably from 3 to 10, more preferably from 3 to 6. Concrete examples of the case where R ^c1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Concrete examples of the case where R ^c1 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^c1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 to 20, and more preferably 2 to 7 carbon atoms. Specific examples of the case where R ^c1 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanonyl group, a 2,2-dimethylpropanoyl group, Heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, Decanoyl group, n-hexadecanoyl group, and the like. Specific examples of the case where R ^c1 is a saturated aliphatic acyloxy group include an acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, , n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, Tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

When R ^c1 is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 to 20, and more preferably 2 to 7 carbon atoms. Specific examples of when R ^c1 is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec- Sec-butyloxycarbonyl, n-pentyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, iso-octyloxycarbonyl, sec-pentyloxycarbonyl, Octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group.

When R ^c1 is a phenylalkyl group, the number of carbon atoms is preferably 7 to 20, more preferably 7 to 10 carbon atoms. When ^Rc1 is a naphthylalkyl group, the number of carbon atoms is preferably from 11 to 20, more preferably from 11 to 14 carbon atoms. Specific examples of the case where R ^c1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^c1 is a naphthylalkyl group include? -Naphthylmethyl group,? -Naphthylmethyl group, 2- (? -Naphthyl) ethyl group and 2- (? -Naphthyl) ethyl group. When R ^c1 is a phenylalkyl group or a naphthylalkyl group, R ^c1 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c1 is a heterocyclyl group, the heterocyclyl group may be a 5-membered or 6-membered monocyclic ring containing 1 or more N, S or O, or a heterocyclyl group in which these monocyclic rings and condensed benzene rings are condensed. And in the case where the heterocyclyl group is a condensed ring, the number of rings is 3. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine , Pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, Ginsenosin, and quinoxaline. When R ^c1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c1 is an amino group substituted with 1 or 2 organic groups, a suitable example of an organic group is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic group having 2 to 20 carbon atoms An acyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, A naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group. Examples of these suitable organic ^groups are the same as R ^c1 . Specific examples of the amino group substituted with 1 or 2 organic groups include a methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- , n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, Naphthoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, .

When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c1 have a substituent further, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 2 to 7 carbon atoms A saturated aliphatic acyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms A morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c1 further have a substituent, the number of the substituent is not limited to the range not hindering the object of the present invention, but is preferably 1 to 4. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^c1 have a plurality of substituents, the plurality of substituents may be the same or different.

R ^c1 is chemically stable but has few steric hindrance and easy synthesis of the oxime ester compound. From the viewpoint that the alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, and the alkylene group having 2 carbon atoms A saturated aliphatic acyl group of 1 to 7 carbon atoms, more preferably an alkyl of 1 to 6 carbon atoms, and particularly preferably a methyl group.

R ^c1 is a position bonded to the phenyl group for the phenyl group, which is bonded R ^c1, the position of the coupling hand of the main skeleton of the phenyl group and the oxime ester compound in the case of the position of the methyl group and the 1-position to a second position, the 4-position , Or 5 position is preferable, and 5 position is more preferable. N1 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

R ^c2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent. When R ^c2 is a carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

In R ^c2 , the substituent group of the phenyl group or the carbazolyl group is not particularly limited within the scope of not impairing the object of the present invention. Examples of suitable substituents which the phenyl group or carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a carbon atom A saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent , A phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, A phenylalkyl group having 7 to 20 atoms, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, A naphthoyloxy group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, 2, an amino group substituted with an organic group, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group.

When R ^c2 is a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 2 to 20 carbon atoms A saturated aliphatic acyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, A naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthocycarbonyl group which may have a substituent, a naphthylalkyl group having a carbon number of 11 to 20 which may have a substituent, A heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent which the phenyl group or carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, , A naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and an amino group substituted by 1 or 2 organic groups are the same as R ^c1 .

In R ^c2 , examples of the substituent when the phenyl group, naphthyl group and heterocyclyl group contained in the substituent group of the phenyl group or the carbazolyl group further have a substituent include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; A phenyl group; Naphthyl group; Benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group of 1 to 6 carbon atoms; A dialkylamino group having an alkyl group of 1 to 6 carbon atoms; Morpholin-1-yl group; Piperazin-1-yl group; halogen; A nitro group; And cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent group of the phenyl group or the carbazolyl group further have a substituent, the number of the substituent is not limited to the extent that the object of the present invention is not impaired, 4 is preferable. When the phenyl group, the naphthyl group, and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

R ^c2 in the following, from an easy point obtaining the photo polymerization initiator has superior sensitivity equation (c2), or and (c3) groups are preferred, more preferably a group represented by the following formula (c2) represented by the following formula (c2) , A group in which A is S is particularly preferable.

[Figure 11]

(R ^c4 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group and a cyano group, A is S or O, and n3 is an integer of 0 to 4.)

[Figure 12]

(R ^c5 and R ^c6 are each a monovalent organic group).

When R ^c4 in the formula (c2) is an organic group, it can be selected from a variety of organic groups as long as the object of the present invention is not impaired. In the formula (c2), when R ^c4 is an organic group, suitable examples include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; A phenyl group; Naphthyl group; Benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group of 1 to 6 carbon atoms; A dialkylamino group having an alkyl group of 1 to 6 carbon atoms; Morpholin-1-yl group; Piperazin-1-yl group; halogen; A nitro group; And cyano group.

Among R ^c4 , a benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A nitro group is preferable, a benzoyl group; A naphthoyl group; A 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; And a 4- (phenyl) phenylcarbonyl group is more preferable.

In the formula (c2), n3 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. if n3 is 1, the binding position of R ^c4 are for the combined hand a phenyl group that is R ^c4 bond with oxygen atom or sulfur atom, preferably in the para position.

R ^c5 in the formula (c3) can be selected from various organic groups within the range not hindering the object of the present invention. Suitable examples of R ^c5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, A phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, A nitro group, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent .

R ^c5 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an ethyl group.

R ^c6 in the formula (c3) is not particularly limited within a range not hindering the object of the present invention, and various organic groups can be selected. Specific examples of the group suitable as R ^c6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclyl group which may have a substituent. As R ^c6 , a phenyl group which may have a substituent among these groups is more preferable, and a 2-methylphenyl group is particularly preferable.

When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, A dialkylamino group having an alkyl group having 1 to 6 atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 further have a substituent, the number of the substituent is not limited as long as it does not impair the object of the present invention, 4 is preferable. When a phenyl group, a naphthyl group, and a heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 have a plurality of substituents, the plurality of substituents may be the same or different.

R ^c3 in the formula (c1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. As R ^c3 , a methyl group or an ethyl group is preferable, and a methyl group is more preferable.

Among the oxime ester compounds represented by the formula (c1), particularly preferred compounds are the following PI-1 to PI-42.

[Figure 13]

[14]

[Figure 15]

[16]

[Figure 17]

[Figure 18]

The oxime ester compound represented by the following formula (c4) is also preferable as a photopolymerization initiator.

[19]

(R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group, R ^c8 and R ^c9 are each a ^straight chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, R ^c8 and R ^c9 is to form a ring by combining to each other, R ^c10 is a monovalent organic group, R ^c11 is an aryl group which may have a number of carbon atoms which may have a hydrogen atom, an optionally substituted alkyl group of 1 to 11, or a substituent group, n4 Is an integer of 0 to 4, and n5 is 0 or 1.)

Here, as the oxime compound for preparing the oxime ester compound of the formula (c4), a compound represented by the following formula (c5) is suitable.

[20]

(R ^c7 , R ^c8 , R ^c9 , R ^c10 , n4 and n5 are the same as in the formula (c4).)

In the formulas (c4) and (c5), R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group. R ^c7 is bonded to a 6-membered aromatic ring which is different from a 6-membered aromatic ring bonded to a group represented by - (CO) _{n5- on the} fluorene ring in the formula (c4). In formula (c4), the bonding position of R ^{c7 to} the fluorene ring is not particularly limited. When the compound represented by the formula (c4) has at least one R ^c7, from the ^viewpoint that the synthesis of the compound represented by the formula (c4) is easy, one of the at least one R ^c7 is bonded at the 2-position of the fluorene ring . When there are a plurality of R ^{c7 s} , a plurality of R ^{c7 s} may be the same or different.

When R ^c7 is an organic group, R ^c7 is not particularly limited as long as it does not impair the object of the present invention, and is appropriately selected from various organic groups. Suitable examples of R ^c7 in the organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, a phenyl group which may have a substituent, A phenoxycarbonyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group , A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, A heterocyclylcarbonyl group which may be substituted, an amino group substituted by an organic group of 1 or 2, a morpholin-1-yl group, There may be mentioned 1-yl group and the like.

When R ^c7 is an alkyl group, the number of carbon atoms of the alkyl group is preferably from 1 to 20, more preferably from 1 to 6. When R ^c7 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of R ^c7 as an alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- n-hexyl group, n-heptyl group, n-octyl group, iso-octyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n- And an isodecyl group. When R ^c7 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c7 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably from 1 to 20, more preferably from 1 to 6. When R ^c7 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ^c7 is an alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec- N-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, isohexyloxy group, isopentyloxy group, sec- tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ^c7 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propoxyoxyethoxyethoxy group, and a methoxy Propyloxy group and the like.

When R ^c7 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or cycloalkoxy group is preferably from 3 to 10, more preferably from 3 to 6. Specific examples of the case where R ^c7 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Concrete examples of the case where R ^c7 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^c7 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. Specific examples of the case where R ^c7 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanonyl group, a 2,2-dimethylpropanoyl group, Heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, Decanoyl group, n-hexadecanoyl group, and the like. Specific examples of when R ^c7 is a saturated aliphatic acyloxy group include an acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2- , n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, Tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

When R ^c7 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably from 2 to 20, more preferably from 2 to 7. Specific examples of when R ^c7 is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec- Sec-butyloxycarbonyl, n-pentyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, iso-octyloxycarbonyl, sec-pentyloxycarbonyl, Octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group.

When R ^c7 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 to 20, more preferably 7 to 10. When R ^c7 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably from 11 to 20, more preferably from 11 to 14. Specific examples of the case where R ^c7 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^c7 is a naphthylalkyl group include an a-naphthylmethyl group, a? -Naphthylmethyl group, a 2- (? -Naphthyl) ethyl group and a 2- (? -Naphthyl) ethyl group. When R ^c7 is a phenylalkyl group or a naphthylalkyl group, R ^c7 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c7 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S or O, or a heterocyclyl group in which the monocyclic ring is condensed with a benzene ring. And in the case where the heterocyclyl group is a condensed ring, the number of rings is 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine , Pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, Piperidine, piperazine, morpholine, tetrahydropyran, tetrahydrofuran, and the like can be given. When R ^c7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c7 is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as the case where R ^c7 is a heterocyclyl group.

When R ^c7 is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic group having 2 to 21 carbon atoms A phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, A naphthylalkyl group having from 11 to 20 carbon atoms which may have a substituent, and heterocyclyl group. A specific example of these suitable organic ^groups is the same as R ^c7 . Specific examples of the amino group substituted with 1 or 2 organic groups include a methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- , n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, Naphthoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, .

The substituent when the phenyl group, naphthyl group and heterocyclyl group contained in R ^c7 have a substituent further includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 2 to 7 carbon atoms A saturated aliphatic acyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms A morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^c7 further have a substituent, the number of the substituent is not limited to the range not hindering the object of the present invention, but is preferably 1 to 4. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^c7 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, it is preferable that R ^{c7 is a} nitro group or a group represented by R ^c12 -CO- since the sensitivity tends to be improved. R ^c12 is not particularly limited as long as the object of the present invention is not impaired, and R ^c12 can be selected from a variety of organic groups. Examples of a group suitable as R ^c12 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclyl group which may have a substituent. As R ^c12 , among these groups, 2-methylphenyl group, thiophen-2-yl group and? -Naphthyl group are particularly preferable.

When R ^c7 is a hydrogen atom, transparency tends to be good, which is preferable. When R ^c7 is a hydrogen atom and R ^c10 is a group represented by the formula (c4a) or (c4b) described later, the transparency tends to be better.

In formula (c4), R ^c8 and R ^c9 each are a straight chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^c8 and R ^c9 may be bonded to each other to form a ring. Among these groups, R ^c8 and R ^c9 are preferably chain alkyl groups which may have a substituent. When R ^c8 and R ^c9 are a straight chain alkyl group which may have a substituent, the straight chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ^c8 and R ^c9 are a ^straight chain alkyl group having no substituent, the number of carbon atoms of the straight chain alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and particularly preferably from 1 to 6. Specific examples of R ^c8 and R ^c9 in the case of a ^straight chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- N-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl , n-decyl group, and isodecyl group. When R ^c8 and R ^c9 are alkyl groups, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c8 and R ^c9 are a ^straight chain alkyl group having a substituent, the number of carbon atoms of the straight chain alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and particularly preferably from 1 to 6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The straight chain alkyl group having a substituent is preferably a straight chain.

The substituent that the alkyl group may have is not particularly limited within the scope of not impairing the object of the present invention. Suitable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of these, a fluorine atom, a chlorine atom and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as those in the case where R ^c7 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group. Specific examples of the heterocyclyl group are the same as those in the case where R ^c7 is a heterocyclyl group. When R ^c7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be straight-chain, branched or straight-chain. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably from 1 to 10, more preferably from 1 to 6.

When the straight chain alkyl group has a substituent, the number of the substituent is not particularly limited. The number of preferred substituents varies depending on the number of carbon atoms of the chain alkyl group. The number of substituents is typically 1 to 20, preferably 1 to 10, and more preferably 1 to 6.

When R ^c8 and R ^c9 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. When R ^c8 and R ^c9 are cyclic organic groups, the substituent that the cyclic organic group may have is the same as when R ^c8 and R ^c9 are ^straight chain alkyl groups.

When R ^c8 and R ^c9 are an aromatic hydrocarbon group, the aromatic hydrocarbon group may be a phenyl group, or a group in which a plurality of benzene rings are bonded to each other through a carbon-carbon bond, or a group in which a plurality of benzene rings are condensed to form. When the aromatic hydrocarbon group is a phenyl group or a group in which a plurality of benzene rings are formed by bonding or condensation, the number of the ring of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited and is preferably 3 or less, more preferably 2 or less, desirable. Specific preferred examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

When R ^c8 and R ^c9 are aliphatic cyclic hydrocarbon groups, aliphatic cyclic hydrocarbon groups may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 10. Examples of the monocyclic cyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobonyl group, a tricyclodecyl group, Tetradecyldodecyl group, adamantyl group, and the like.

When R ^c8 and R ^c9 are a heterocyclyl group, the heterocyclyl group may be a 5-membered or 6-membered monocyclic ring containing one or more N, S, O, or a monocyclic or bicyclic monocyclic ring containing one or more of these monocyclic rings, . And in the case where the heterocyclyl group is a condensed ring, the number of rings is 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine , Pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, Piperidine, piperazine, morpholine, tetrahydropyran, tetrahydrofuran, and the like can be given.

R ^c8 and R ^c9 may be bonded to each other to form a ring. The group consisting of rings formed by R ^c8 and R ^c9 is preferably a cycloalkylidene group. When R ^c8 and R ^c9 are combined to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered to 6-membered ring, more preferably a 5-membered ring.

When the group formed by combining R ^c8 and R ^c9 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring which may be condensed with a cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, And pyrimidine rings, and the like.

Among the groups R ^c8 and R ^c9 described above, examples of suitable groups include groups represented by the formula -A ¹ -A ² . In the formula, A ¹ is a straight chain alkylene group, and A ² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The number of carbon atoms of the straight chain alkylene group of A ¹ is preferably from 1 to 10, more preferably from 1 to 6. When A ² is an alkoxy group, the alkoxy group may be linear or branched or straight-chain. The number of carbon atoms of the alkoxy group is preferably from 1 to 10, more preferably from 1 to 6. When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable. When A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom, a chlorine atom or a bromine atom. The halogenated alkyl group may be straight chain or branched chain, and straight chain is preferable. When A ² is a cyclic organic group, examples of cyclic organic groups are the same as cyclic organic groups having R ^c8 and R ^c9 as substituents. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group having R ^c8 and R ^c9 as a substituent.

Suitable examples of R ^c8 and R ^c9 include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group and n-octyl group; Methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, Ethoxy-n-hexyl group, 7-ethoxy-n-heptyl group, and 8-ethoxy-n-octyl group; N-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano- n-heptyl group, and 8-cyano-n-octyl group; Phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, And a phenylalkyl group such as an 8-phenyl-n-octyl group; Cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl n-hexyl group, 7-cyclohexyl cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, Cycloalkylalkyl groups such as a t-butyl group, a 6-cyclopentyl-n-hexyl group, a 7-cyclopentyl-n-heptyl group and an 8-cyclopentyl-n-octyl group; Methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl- Ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, An alkoxycarbonylalkyl group such as an ethoxycarbonyl-n-octyl group; Chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro- n-heptyl group, Propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo- hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5, And a 5-heptafluoro-n-pentyl group.

Among the groups suitable as R ^c8 and R ^c9 among the above groups, preferred are groups selected from the group consisting of an ethyl group, an n-propyl group, an n-butyl group, a n-pentyl group, a 2- methoxyethyl group, a 2-cyanoethyl group, A 2-chloroethyl group, a 2-bromoethyl group, a 3,3,3-trifluoropropyl group, and a 3,3,4,4,5,5,5-heptafluoro- pentyl group.

Of R ^c10 suitable organic group for example in the same manner as R ^c7, an alkyl group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a substituent A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a substituent A naphthoyl group which may have a substituent, a naphthoylcarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocycle which may have a substituent A heterocyclylcarbonyl group which may have a substituent, an amino group substituted by an organic group of 1 or 2, a morpholin-1-yl group, And a piperazin-1-yl group. Specific examples of these groups are as described for R ^c7 . As R ^c10 , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on an aromatic ring, and a phenylthioalkyl group which may have a substituent on an aromatic ring are also preferable. Phenoxy group, and the substituent group which may have a phenylthio group is the same as the substituent which may have a phenyl group contained in R ^c7.

Among the organic groups, R ^{c10 is preferably an} alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group or a phenylthioalkyl group which may have a substituent on an aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably from 1 to 8, more preferably from 1 to 4, and particularly preferably 2. [ Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferable. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2- (4-chlorophenylthio) ethyl group is preferable.

Further, as R ^c10, it is preferable airway represented by -A ³ -CO-OA ^4. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and is preferably an alkylene group. A ⁴ is a monovalent organic group and is preferably a monovalent hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be linear or branched or straight-chain. When A ³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably from 1 to 10, more preferably from 1 to 6, and particularly preferably from 1 to 4.

Suitable examples of A ⁴ include an alkyl group of 1 to 10 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, and an aromatic hydrocarbon group of 6 to 20 carbon atoms. Suitable examples of A ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- Naphthyl group, benzyl group, phenethyl group,? -Naphthylmethyl group, and? -Naphthylmethyl group.

Specific examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n-butyloxycarbonyl Ethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl- Propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl- n-propyl group, 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group and 3-phenoxycarbonyl-n-propyl group.

Above it has been described for the R ^c10, R ^c10 is preferably a group represented by the following formula (c4a) or (c4b) As.

[Figure 21]

(In the formulas (c4a) and (c4b), R ^c13 and R ^c14 are each an organic group, n6 is an integer of 0 to 4, and when R ^c13 and R ^c14 are present at adjacent positions on the benzene ring, R ^c13 and R ^c14 is to form a ring by combining to each other, n7 is an integer of 1 ~ 8, n8 represents an integer of 1 ~ 5, n9 is an integer of 0 ~ (n8 + 3), R c15 is an organic group.)

An example of an organic ^group for R ^c13 and R ^c14 in formula (c4a) is the same as R ^c7 . As R ^{c13, an} alkyl group or a phenyl group is preferable. When R ^c13 is an alkyl group, the number of carbon atoms is preferably from 1 to 10, more preferably from 1 to 5, particularly preferably from 1 to 3, most preferably 1. In other words, R ^c13 is most preferably a methyl group. When R ^c13 and R ^c14 are bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. Suitable examples of the group represented by the formula (c4a) in which R ^c13 and R ^c14 form a ring include naphthalene-1-yl group, 1,2,3,4-tetrahydronaphthalen-5- . In the formula (c4a), n6 is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the formula (c4b), R ^c15 is an organic group. The organic group may be the same group as the organic group described for R ^c7 . Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, and particularly preferably from 1 to 3. As R ^c15 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

In the formula (c4b), n8 is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2. In the formula (c4b), n9 is 0 to (n8 + 3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0. In the formula (c4b), n7 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

In the formula (c4), R ^c11 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As the substituent which R ^c11 may be an alkyl group, a phenyl group, a naphthyl group and the like are preferably exemplified. The substituent which may be taken when R ^c7 is an aryl group is preferably an alkyl group, an alkoxy group or a halogen atom having 1 to 5 carbon atoms.

In the formula (c4), R ^{c11 is preferably a} hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a n-butyl group, a phenyl group, a benzyl group, a methylphenyl group or a naphthyl group, A methyl group or a phenyl group is more preferable.

The compound represented by the formula (c4) is a step for converting an oxime group (> C = N-OH) contained in the compound represented by the above formula (c5) into an oxime ester group represented by> ^C═NO- ≪ / RTI > R ^c11 and R ^c11 are the same in the formula (c4).

Conversion of the oxime group (> C = N-OH) to the oxime ester group represented by> ^C═NO -COR ^c11 is carried out by reacting the compound represented by the formula (c5) described above with an acylating agent.

Acylating agents giving an acyl group represented by -COR ^c11 include an acid anhydride represented by (R ^c11 CO) ₂ O and an acid halide represented by R ^c11 COHal (Hal is a halogen atom).

Suitable specific examples of the compound represented by the formula (c4) include the following PI-43 to PI-83.

[22]

[23]

The content of the photopolymerization initiator (C) is preferably 0.5 to 30% by mass, and more preferably 1 to 20% by mass with respect to the mass of the total solid content of the resin composition. By setting the content of the photopolymerization initiator (C) within the above range, it is possible to obtain a resin composition which is less prone to pattern defects.

The photopolymerization initiator (C) may be combined with a photopolymerization initiator. Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, benzoic acid Dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10 Diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2- mercaptobenzooxazole, 2- mercaptobenzoimidazole, 2- Thiol compounds such as benzothiazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, pentaerythritol tetramercaptoacetate, and 3-mercaptopropionate. These photoinitiators may be used alone or in combination of two or more.

≪ Pigment (D) >

The resin composition contains the pigment (D). The pigment (D) is not particularly limited. For example, a compound classified as a pigment in a color index (CI, published by The Society of Dyers and Colourists), specifically, a color index ) Number can be used.

Examples of suitable yellow pigments include C.I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and only the numbers are described below), 3,11,12,13,14,15,16,17,20,24,31,35,55,60 , 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, , 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, .

Examples of suitable orange pigments include C.I. Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same and only the numbers are described), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51 , 55, 59, 61, 63, 64, 71, and 73, respectively.

Examples of suitable purple pigments include C.I. Pigment Violet 1 (hereinafter, the same is true of C. I. Pigment Violet), and only numbers are given), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40,

Examples of suitable red pigments include C.I. 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 49: 1, 49: 1, 48: 2, 48: 3, 48: 4, 49: 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264 and 265.

Examples of suitable blue pigments include C.I. Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same and only numbers are listed), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, .

Examples of pigments of other colors which can be suitably used include C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Green pigments such as Pigment Green 37, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Brown pigments such as Pigment Brown 28, C.I. Pigment Black 1, C.I. Pigment Black 7 and the like.

It is also preferable that the resin composition contains a black pigment as the pigment (D). By using a resin composition containing a black pigment, the cured film to be formed is provided with light shielding property. Therefore, the resin composition containing a black pigment is suitably used for forming a black matrix or a black column spacer in a liquid crystal display panel or for forming a bank for partitioning a light emitting layer in an organic EL device.

Examples of the black pigment include metal oxides, complex oxides, metal sulfides, metal sulfates or metal oxides such as carbon black, perylene pigments, lactam pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, Carbonates, organic, and inorganic pigments. Among these black pigments, carbon black is preferable because it is easy to obtain, but it is easy to form a cured film having excellent light shielding property and high electric resistance.

The color of the black pigment is not limited to black, which is an achromatic color in the color scheme, but may be a violet black, a blue colored black, or a red colored black.

As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used. Resin-coated carbon black may also be used.

As the carbon black, carbon black to which an acidic group is introduced is also preferable. The acid group introduced into the carbon black is a functional group which shows acidity as defined by Brensted. Specific examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The acid group introduced into the carbon black may form a salt. The cation forming the acidic group and the salt is not particularly limited within the range not hindering the object of the present invention. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions and the like, and alkali metal ions such as sodium ion, potassium ion and lithium ion, and ammonium ion are preferable.

Among the carbon black treated by introducing the acid group described above, it is preferable to use a carboxylic acid group, a carboxylic acid group, a sulfonic acid group, and a sulfonic acid group from the group consisting of a carboxylic acid group, a sulfonic acid group, and a sulfonic acid group from the viewpoint of achieving high resistance of the light- Carbon black having at least one functional group selected is preferable.

The method of introducing an acidic group into carbon black is not particularly limited. Examples of the method for introducing an acidic group include the following methods.

1) A method of introducing a sulfonic acid group into a carbon black by a direct substitution method using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or the like, or an indirect substitution method using a sulfite or a bisulfite hydrogen salt.

2) A method of diazotizing a carbon black with an organic compound having an amino group and an acidic group.

3) A method of reacting an organic compound having a halogen atom and an acidic group and carbon black having a hydroxyl group by the Williamson etherification method.

4) A method of reacting an organic compound having a halocarbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group.

5) A method of deprotecting a carbon black with an Friedel-Crafts reaction using an organic compound having a halocarbonyl group and an acid group protected by a protecting group.

Among these methods, the method 2) is preferable because the introduction of the acidic group is easy and safe. As the organic compound having an amino group and an acidic group used in the method 2), a compound in which an amino group and an acidic group are bonded to an aromatic group is preferable. Examples of such compounds include aminobenzenesulfonic acids such as sulfanilic acid and aminobenzoic acids such as 4-aminobenzoic acid.

The number of moles of the acid group introduced into the carbon black is not particularly limited within the range not hindering the object of the present invention. The number of moles of the acid group introduced into the carbon black is preferably 1 to 200 mmol, more preferably 5 to 100 mmol, per 100 g of carbon black.

The carbon black into which the acidic group has been introduced may be coated with a resin. When a resin composition containing carbon black coated with a resin is used, it is easy to form a light-shielding cured film having excellent light-shielding properties and insulation properties and a low surface reflectance. Further, by the coating treatment with the resin, adverse effects on the dielectric constant of the light-shielding cured film formed by using the resin composition do not particularly occur. Examples of the resin that can be used for coating carbon black include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glidant resin, epoxy resin and alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, Polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone, polybutylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, And a thermoplastic resin such as ketone. The covering amount of the resin with respect to the carbon black is preferably from 1 to 30 mass% with respect to the sum of the mass of the carbon black and the mass of the resin.

As the black pigment, a perylene pigment can be preferably used. Specific examples of the perylene pigments include perylene pigments represented by the following formula (d-1), perylene pigments represented by the following formula (d-2), and perylene pigments represented by the following formula (d-3) . As commercial products, products such as K0084 and K0086, Pigment Black 21, 30, 31, 32, 33, and 34 manufactured by BASF Co., Ltd. can be preferably used as a perylene pigment.

[24]

In formula (d-1), R ^d1 and R ^d2 each independently represent an alkylene group having 1 to 3 carbon atoms, and R ^d3 and R ^d4 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group or an acetyl group .

[25]

In the formula (d-2), R ^d5 and R ^d6 each independently represent an alkylene group having 1 to 7 carbon atoms.

[26]

In the formula (d-3), R ^d7 and R ^d8 are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, and may contain a hetero atom of N, O, S, or P. When R ^d7 and R ^d8 are alkyl groups, the alkyl groups may be linear or branched.

Examples of the compound represented by the formula (d-1), the compound represented by the formula (d-2), and the compound represented by the formula (d-3) Can be synthesized by the method described in Japanese Unexamined Patent Publication No. 63-26784. Namely, a heating reaction is carried out in water or an organic solvent using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines as raw materials. The desired product can be obtained by reprecipitation of the obtained preparation into sulfuric acid or recrystallization in water, an organic solvent or a mixed solvent thereof.

In order to disperse the perylene pigment in the resin composition well, the average particle diameter of the perylene pigment is preferably 10 to 1000 nm.

As the light-shielding agent, a lactam-based pigment may be included. Examples of the lactam-based pigment include compounds represented by the following formula (d-4).

[Figure 27]

In the formula (d-4), X ^d represents a double bond, and each of Ge isomers is independently E or Z form, and each R ^d9 independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, R ^d10 independently represents a hydrogen atom, a methyl group, or a phenyl group, and R ^d11 each independently represents a hydrogen atom, a methyl group, or a chlorine atom.

The compounds represented by the formula (d-4) may be used alone or in combination of two or more.

R ^d9 is preferably bonded to the 6-position of the dihydroindolone ring from the viewpoint of easy production of the compound represented by the formula (d-4), and R ^d11 is preferably bonded to the 4-position of the dihydroindolone ring Do. From the same viewpoint, R ^d9 , R ^d10 , and R ^d11 are preferably hydrogen atoms.

The compound represented by the formula (d-4) has an EE, ZZ, or EZ form as a geometric isomer, but may be any of these single compounds or a mixture of these geometric isomers.

The compound represented by the formula (d-4) can be produced, for example, by the method described in International Publication No. 2000/24736 and International Publication WO01081624.

In order to disperse the lactam-based pigment well in the resin composition, the average particle diameter of the lactam-based pigment is preferably 10 to 1000 nm.

In addition, fine particles mainly composed of silver (AgSn) tin (hereinafter referred to as " AgSn alloy fine particles ") are also preferably used as black pigments. The AgSn alloy fine particles may be a main component of the AgSn alloy, and the other metal components may include, for example, Ni, Pd, Au, and the like.

The average particle diameter of the AgSn alloy fine particles is preferably 1 to 300 nm.

When the AgSn alloy is represented by the chemical formula AgxSn, the range of x in which a chemically stable AgSn alloy is obtained is 1? X? 10, and the range of x in which the chemical stability and the degree of blackness are simultaneously obtained is 3?

Here, when the mass ratio of Ag in the AgSn alloy is obtained in the range of x,

When x = 1, Ag / AgSn = 0.4762

When x = 3, 3 · Ag / Ag 3 Sn = 0.7317

When x = 4, 4 · Ag / Ag4Sn = 0.7843

When x = 10, 10? Ag / Ag10Sn = 0.9008

.

Therefore, this AgSn alloy is chemically stable when containing Ag in an amount of 47.6 to 90 mass%, and when Ag is contained in an amount of 73.17 to 78.43 mass%, chemical stability and blackness can be effectively obtained with respect to the amount of Ag.

The AgSn alloy fine particles can be produced by a conventional method of synthesizing fine particles. Examples of the method for synthesizing fine particles include a vapor phase reaction method, a spray pyrolysis method, an atomization method, a liquid phase reaction method, a freeze drying method, and a hydrothermal synthesis method.

The AgSn alloy fine particles have a high insulating property, but depending on the use of the resin composition, the surface may be covered with an insulating film in order to further increase the insulating property. As a material of such an insulating film, a metal oxide or an organic polymer compound is suitable.

As the metal oxide, a metal oxide having an insulating property such as silicon oxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), yttrium oxide (yttria), titanium oxide (titania) and the like are suitably used.

As the organic polymer compound, a resin having an insulating property, for example, polyimide, polyether, polyacrylate, polyamine compound and the like are suitably used.

The thickness of the insulating film is preferably 1 to 100 nm, more preferably 5 to 50 nm in order to sufficiently increase the insulating property of the surface of the AgSn alloy fine particles.

The insulating film can be easily formed by a surface modification technique or a surface coating technique. In particular, the use of an alkoxide such as tetraethoxysilane or aluminum triethoxide is preferable because an insulating film having a uniform film thickness can be formed at a relatively low temperature.

As the black pigment, the above-mentioned perylene-based pigment, lactam-based pigment and AgSn alloy fine particles may be used singly or in combination.

In addition, the black pigment may contain pigments of hue such as red, blue, green, and sulfur for the purpose of adjusting the color tone. The pigment of another color of the black pigment can be appropriately selected from known pigments. For example, various pigments described above can be used as pigments of other colors of black pigments. The amount of the pigment of another color of the black pigment is preferably 15 mass% or less, more preferably 10 mass% or less, based on the total mass of the black pigment.

In order to uniformly disperse the above-described pigment (D) in the resin composition, a dispersing agent may be further used. As such a dispersing agent, it is preferable to use a polymeric dispersant of polyethylene imine type, urethane resin type or acrylic resin type. Particularly when carbon black is used as the pigment (D), it is preferable to use an acrylic resin-based dispersing agent as the dispersing agent.

In addition, corrosive gas resulting from the dispersing agent may be generated from the cured film. For this reason, it is also an example of a preferred embodiment that the pigment (D) is subjected to dispersion treatment without using a dispersant.

The inorganic pigments and the organic pigments may be used alone or in combination of two or more. When used in combination, it is preferable to use the organic pigments in an amount of 10 to 80 parts by mass based on 100 parts by mass of the total amount of the inorganic pigments and the organic pigments, More preferably 20 to 40 parts by mass.

Further, in the resin composition, the pigment (D) and the dye may be used in combination. This dye may be appropriately selected from known materials.

Examples of the dyes applicable to the resin composition include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, etc. .

These dyes may be dispersed in an organic solvent or the like by lakening (coagulation) and used as the colorant (D).

In addition to these dyes, dyes and the like described in, for example, JP-A-2013-225132, JP-A-2014-178477, JP-A-2013-137543, JP-A-2011-38085, JP-A-2014-197206 Can be preferably used.

The amount of the pigment (D) to be used in the resin composition may be appropriately selected within a range not to impair the object of the present invention. Typically, the amount is preferably 2 to 75% by mass, And more preferably 70% by mass.

It is preferable to add the pigment (D) to the resin composition after preparing a dispersion in which the pigment (D) is dispersed at a suitable concentration in the presence or absence of the dispersant.

In the present specification, the amount of the pigment D used can be defined as a value including the dispersing system present therein.

≪ Silane coupling agent (E) >

The resin composition includes a silane coupling agent (E).

The silane coupling agent (E) is represented by the following formula (e1):

(R ^e1 ) _a (R ^e2 ) _3-a Si-R ^e3 -NH-CO-R ^e4 -R ^e5 (e1)

(In the formula (e1), R ^e1 and R ^e2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, a is 2 or 3, R ^e3 is an alkylene group having 1 to 10 carbon atoms, R ^e4 Is a bivalent organic group and R ^e5 is a Bronsted acid group, an alcoholic hydroxyl group, an amino group, or a carbamoyl group.)

Lt; / RTI >

When the patterning by the photolithography method is carried out using the resin composition by blending the silane coupling agent containing the compound represented by the above formula (e1) into the resin composition, the patterned cured film formed is favorably adhered to the substrate It is possible to suppress the occurrence of development residue in the unexposed portion.

In the formula (e1), R ^e1 and R ^e2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms.

Suitable examples of the hydrocarbon group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- A hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a phenyl group.

Of these, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a phenyl group are preferable, and a methyl group and an ethyl group are more preferable.

In the formula (e1), R ^e3 is an alkylene group having 1 to 10 carbon atoms. The alkylene group as R ^e3 may be linear or branched, and is preferably straight-chain.

Suitable specific examples of R ^e3 include methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, Diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, and a decane-1,10-diyl group.

Among these, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,2-diyl group, propane-1,2-diyl group and the like are preferable because of easy acquisition and synthesis of the compound represented by formula (e1) , A 3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group and a hexane-1,6-diyl group are preferable, and an ethane- A di-yl group and a butane-1,4-diyl group are more preferable, and a propane-1,3-diyl group is particularly preferable.

In the formula (e1), R ^e5 is a Bronsted acid group, an alcoholic hydroxyl group, an amino group (-NH ₂ ), or a carbamoyl group (-CO-NH ₂ ).

Since these groups are liable to form hydrogen bonds, the groups represented by -CO-R ^e4 -R ^e5 at the end of the compound represented by the formula (e1) bonded to the substrate surface are blocked by hydrogen bonding easy.

It is considered that the blocks formed by the groups represented by -CO-R ^e4 -R ^e5 prevent the development residue from being strongly bonded to the substrate surface in the unexposed portion, and the development residue is inhibited.

Further, the group represented by -CO-R ^e4 -R ^e5 tends to form a hydrogen bond with the cured film. Therefore, it is considered that the cured film formed using the resin composition containing the compound represented by the formula (e1) adheres well to the substrate surface.

Suitable specific examples of the Brensted acid group as R ^e5 include a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, a phosphinic acid group, and a phenolic hydroxyl group.

Among R ^e5 , a Bronsted acid group is preferable, and a carboxyl group is more preferable from the viewpoint of obtaining a desired effect.

The divalent organic group as R ^e4 is not particularly limited within the scope of not impairing the object of the present invention. The number of carbon atoms of the divalent organic group as R ^e4 is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less, particularly preferably 1 or more and 12 or less.

^Examples of the divalent organic group as R ^e4 include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, and a divalent heterocyclic group.

These groups may all have a substituent.

When the divalent aliphatic hydrocarbon group, divalent aromatic hydrocarbon group and divalent heterocyclic group as R ^e4 have a substituent, suitable examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, A dialkylamino group having an alkyl group having 1 to 6 atoms, a halogen, a nitro group, and a cyano group.

The bivalent aliphatic hydrocarbon group as R ^e4 may be straight chain, branched chain, cyclic, cyclic, or a combination of these structures.

The bivalent aliphatic hydrocarbon group as R ^e4 may contain an unsaturated double bond.

Suitable examples of the divalent aliphatic hydrocarbon group as R ^{e4 in the} chain are methylene, ethane-1,2-diyl, ethene-1,2-diyl, propane-1,3-diyl, Diyl group, a propane-2,2-diyl group, and a butane-1,4-diyl group.

When the divalent aliphatic hydrocarbon group as R ^e4 is cyclic, preferred groups include groups excluding two hydrogen atoms from monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane, and the like.

Specific examples include monocycloalkane such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and monocycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane, .

Suitable examples of the divalent aromatic hydrocarbon group as R ^e4 include a phenylene group, a naphthalene diyl group, a phenanthrene diyl group, an anthracenediyl group, and a pyrandiyl group.

When R ^e4 is a divalent heterocyclic group, the heterocyclic group may be a 5-membered or 6-membered monocyclic ring containing 1 or more N, S or O, or a group obtained by condensing these monocyclic rings with a benzene ring.

Examples of such divalent heterocyclic groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, Benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, , And groups derived from quinoxaline and the like excluding two hydrogen atoms.

As R ^e4 , a bivalent aromatic hydrocarbon group is preferable from the viewpoint of the effect of pattern adhesion and the effect of suppressing the development residue.

In the bivalent aromatic hydrocarbon group, the relationship between the position of the carbon atom to which one hand is bonded and the position of the carbon atom to which the other hand is bonded is preferably an adjacent position or a ferry position.

The Bronsted acid group, alcoholic hydroxyl group, amino group, or carbamoyl group as R ^e5 is a functional group capable of forming a hydrogen bond with a carbonyl group.

For this reason, in a bivalent aromatic hydrocarbon group, when the relationship between the position of a carbon atom to which one bonding hand is bonded and the position of a carbon atom to which the other bonding hand is bonded is an adjacent position or a ferry position, when the compounds represented by (e1), bonded to adjacent positions on the substrate, the R ^e5 of the compound of formula (e1), is easy to form a carbonyl group and the hydrogen bond in the compounds represented by other formula (e1).

On the other hand, when the compound represented by the formula (e1) is bound to a position close to the substrate, since R ^e4 is a bivalent aromatic group, π-π stacking or the like may occur between the plurality of R ^e4 .

For the reasons described above, when the positional relationship of the two bonded hands in the bivalent aromatic hydrocarbon group is in the adjacent position or in the relation of the ferry position, -CO-R ^e4 -R ^{e5 at} the terminal of the compound represented by the formula (e1) Is likely to exhibit self-organizing behavior, and it is presumed that a plurality of blocks consisting of groups represented by -CO-R ^e4 -R ^e5 are likely to be formed on the surface of the substrate.

In this case, the cured film is favorably adhered to the substrate by the hydrogen bonding between the cured film and the aromatic rings and the interaction of the aromatic rings with each other in the exposed part of the block ^composed of the group represented by -CO-R ^e4 -R ^e5 , In the light portion, it is considered that the direct interaction between the substrate and the development residue is inhibited and the occurrence of the development residue is suppressed.

Suitable examples of the divalent aromatic hydrocarbon group as R ^e4 include an aromatic hydrocarbon group such as o-phenylene group, m-phenylene group, p-phenylene group, naphthalene-1,2-diyl group, naphthalene- A naphthalene-1,6-diyl group, a naphthalene-1,6-diyl group, a naphthalene-1,8-diyl group, a naphthalene- Naphthalene-2,6-diyl group, and naphthalene-2,7-diyl group.

Among these groups, an o-phenylene group, a naphthalene-1,2-diyl group, a naphthalene-2,3-diyl group, or a naphthalene-1,8-diyl group is preferable.

As described above, in the bivalent aromatic hydrocarbon group, the relationship between the position of the carbon atom to which one hand is bonded and the position of the carbon atom to which the other hand is bonded is preferably an adjacent position or a ferry position .

Suitable specific examples of the compound represented by the formula (e1) include the following compounds.

[28]

The compound represented by the formula (e1) described above can be used in combination with various silane coupling agents having a structure other than the structure represented by the formula (e1). As the silane coupling agent usable with the compound represented by the formula (e1), a silane coupling agent conventionally used for various purposes can be appropriately selected.

Suitable examples of such silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyl Monoalkyltrialkoxysilanes such as trimethoxysilane and n-butyltriethoxysilane; Dialkyldialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; Monophenyl trialkoxysilane such as phenyltrimethoxysilane and phenyltriethoxysilane; Diphenyldialkoxysilane such as diphenyldimethoxysilane and diphenyldiethoxysilane; Monovinyl trialkoxysilane such as vinyltrimethoxysilane and vinyltriethoxysilane; (Meth) acryloxy compounds such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropylmethyldiethoxysilane. Alkyl monoalkyl dialkoxysilanes; (Meth) acryloxyalkyltrialkoxysilane such as 3-acryloxypropyltrimethoxysilane; Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) (Aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-2- 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3- Amino group-containing tri (or di) alkoxysilanes such as aminopropyltriethoxysilane and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane; And ketimine silanes in which these amino groups are protected with aldehyde or the like; (Or di) alkoxysilanes containing non-cyclic epoxy fluorenylidene groups such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and 3-glycidoxypropylmethyldimethoxysilane, ; Non-cyclic epoxy group-containing alkylmonoalkyldialkoxysilanes such as 3-glycidoxypropylmethyldiethoxysilane; 2- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl triethoxysilane, 2- (3,4- Alkyl tri (or di) alkoxy silanes containing an alicyclic epoxy group such as 2- (3,4-epoxycyclohexyl) methyldiethoxy silane; Alkylmonoalkyl dialkoxysilanes containing an alicyclic epoxy group such as 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane; Containing alkyltrialkoxysilanes such as [(3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane and [(3-ethyl-3-oxetanyl) methoxy] propyltriethoxysilane Silane; Mercaptoalkyltrialkoxysilanes such as 3-mercaptopropyltrimethoxysilane; Mercaptoalkylmonoalkyldialkoxysilanes such as 3-mercaptopropylmethyldimethoxysilane; Ureido alkyltrialkoxysilanes such as 3-ureidopropyltriethoxysilane; Isocyanate alkyltrialkoxysilanes such as 3-isocyanatopropyltriethoxysilane; Isocyanurate-containing trialkoxysilanes such as tris- (trimethoxysilylpropyl) isocyanurate and tris- (triethoxysilylpropyl) isocyanurate; 3-trimethoxysilylpropyl succinic anhydride, other acid anhydride groups (e.g., cyclohexanedicarboxylic acid anhydride group, 4-methyl-cyclohexanedicarboxylic anhydride group, 5-methyl-cyclohexanedicarboxylic acid anhydride group, Cycloheptane dicarboxylic acid anhydride group, 7-oxa-bicycloheptanedicarboxylic acid anhydride group, phthalic acid anhydride group, etc.), trialkoxysilane or the like, an acid anhydride group-containing alkyltrialkoxysilane; A cyclohexanedicarboxylic acid group, or a half ester group thereof, a 4-methyl-cyclohexanedicarboxylic acid group, or a half ester group thereof, a 5-methyl-cyclohexanedicarboxylic acid group, or a Containing alkyltrialkoxysilane having a carboxyl group, a half ester group, a bicycloheptanedicarboxylic acid group or a half ester group thereof, a 7-oxa-bicycloheptanedicarboxylic acid group, or a half ester group, a phthalic acid group or a half ester group thereof ; N-tert-butyl-3- (3-trimethoxysilylpropyl) succinic acid imide and other imide group-containing alkyltrialkoxysilanes; (3-trimethoxysilylpropyl) -t-butylcarbamate, and (3-triethoxysilylpropyl) -tert-butylcarbamate; And the like.

The content of the silane coupling agent (E) in the resin composition is preferably 0.01 to 10% by mass, more preferably 0.5 to 6% by mass, particularly preferably 1 to 5% by mass, based on the mass of the entire solid content of the resin composition Do.

By using the positive silane coupling agent (E) within such a range, the pattern to be formed is easily adhered particularly well to the substrate and the generation of the development residue in the unexposed area can be suppressed particularly.

The ratio of the mass of the compound represented by the formula (e1) to the total mass of the silane coupling agent (E) is preferably 10 mass% or more, more preferably 15 mass% or more, and particularly preferably 30 mass% or more Do.

The upper limit of the mass ratio of the compound represented by the formula (e1) to the total mass of the silane coupling agent (E) is not particularly limited, but may be, for example, 95 mass% or less and 90 mass% or less And may be 85% by mass or less.

The ratio of the mass of the compound represented by the formula (e1) to the total mass of the silane coupling agent (E) may be 100% by mass.

By using the compound represented by the formula (e1) in the above range in a ratio as described above by using the silane coupling agent (E), the pattern to be formed is easily adhered well to the substrate and the occurrence of development residue .

Further, in the resin composition, the content of the compound represented by the formula (e1) is preferably 0.01 to 10% by mass, more preferably 0.5 to 6% by mass, more preferably 1 to 5% by mass based on the mass of the total solid content of the resin composition. % By mass is particularly preferable.

By using the compound represented by the formula (e1) in this range, the pattern to be formed is easily adhered particularly well to the substrate, and the occurrence of the development residue in the unexposed area can be suppressed particularly.

≪ Organic solvent (S) >

The resin composition preferably contains an organic solvent (S) in order to improve the coating property and adjust the viscosity.

Specific examples of the organic solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether , Tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and the like (Poly) alkylene glycol monoalkyl ethers; (Propylene glycol monomethyl ether acetate), ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA) Alkylene glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, Propyl acetate, isopropyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, benzyl acetate, n-butyl propionate, ethyl butyrate, , Other esters such as methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; N, N-dimethylacetamide, N, N-dimethylisobutylamide, N, N-diethylacetamide, N, N-diethyl Nitrogen-containing polar organic solvents such as formamide, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, pyridine, and N, N, N ', N'-tetramethylurea; And the like.

Of these, alkylene glycol monoalkyl ether acetates, alkylene glycol monoalkyl ether acetates, the above-mentioned other ethers, lactic acid alkyl esters and the above-mentioned other esters are preferable, and alkylene glycol monoalkyl ether acetates, One of the other ethers, and the other ester described above such as benzyl acetate are more preferable.

It is also preferable that the organic solvent (S) contains a nitrogen-containing polar organic solvent in view of the solubility of each component and the dispersibility of the pigment (D). As the nitrogen-containing polar organic solvent, N, N, N ', N'-tetramethylurea and the like can be used.

These solvents may be used alone or in combination of two or more.

The content of the organic solvent (S) is not particularly limited and is appropriately set in accordance with the coating film thickness at a concentration applicable to a substrate or the like. The viscosity of the resin composition is preferably 5 to 500 cp, more preferably 10 to 50 cp, and even more preferably 20 to 30 cp. The solid concentration is preferably 5 to 100% by mass, and more preferably 15 to 50% by mass.

≪ Other components >

Additives such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, a defoaming agent, and an epoxy compound may be contained in the resin composition, if necessary. Any additive may be any conventionally known one.

Examples of the surfactant include anionic, cationic and nonionic surfactants. Examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether. Examples of the defoaming agent include silicon compounds and fluorine compounds .

≪ Preparation method of resin composition >

The resin composition described above is obtained by mixing each of the above components in a predetermined amount and then uniformly mixing the mixture with an agitator. It may also be filtered using a filter so that the resulting mixture becomes more uniform.

≪ Process for producing cured film &

As a method for producing a cured film, a conventionally known method for producing a cured film using a resin composition containing a photopolymerizable compound (B) can be employed without particular limitation.

As a suitable production method of the cured film,

A step of forming a coating film by applying the resin composition described above,

A step of positionally selectively exposing the coating film,

A step of developing the exposed coated film to form a patterned cured film,

And a step of baking the patterned cured film.

In order to form a cured film using the resin composition, a resin composition is first applied on a substrate selected according to the use of the cured film to form a coated film. The method of forming the coating film is not particularly limited, but is carried out using a non-contact type coating device such as a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, a spinner (rotary coating device), or a curtain flow coater.

The applied resin composition is dried as needed to constitute a coating film. The drying method is not particularly limited and includes, for example, (1) a method of drying on a hot plate at a temperature of 80 to 120 ° C, preferably 90 to 100 ° C for 60 to 120 seconds, (2) (3) a method of removing the solvent by putting it in a warm air heater or an infrared heater for several minutes to several hours, and the like.

Then, the coating film is exposed. Exposure is carried out by irradiating active energy rays such as ultraviolet rays and excimer laser rays. The exposure is performed in a positional manner by, for example, a method of performing exposure through a mask of a negative type. The energy dose to be irradiated varies depending on the composition of the resin composition, but is preferably about 40 to 200 mJ / cm ² , for example.

When the entire surface of the coating film is exposed, a non-patterned cured film having a shape corresponding to the shape of the coating film is formed.

When the coating film is selectively exposed, the unexposed area is dissolved and removed in the developing solution by developing the exposed film with a developing solution to form a patterned cured film. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. The developer is appropriately selected depending on the composition of the resin composition. As the developer, a basic aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt or the like can be used.

Then, the patterned cured film is baked (post-baked). The baking temperature is not particularly limited, but is preferably 180 to 250 占 폚, more preferably 220 to 230 占 폚. The baking time is typically 10 to 90 minutes, preferably 20 to 60 minutes.

By baking as described above, a cured film of the resin composition is obtained.

The colored cured film including the pigment (D) thus formed can be suitably used as a black matrix in a color filter or a coloring film such as RGB depending on the color of the pigment (D).

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples.

[Preparation Example 1]

First, 235 g of a bisphenol fluorene epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol and 72.0 g of acrylic acid And the mixture was heated and dissolved at 90 to 100 ° C while blowing air at a rate of 25 ml / min. Then, the temperature was gradually raised while the solution was cloudy, and the solution was completely dissolved by heating at 120 ° C. At this time, the solution gradually became a transparent point group, but stirring was continued. In the meantime, the acid value was measured, and heating stirring was continued until it was less than 1.0 mg KOH / g. The acid value required 12 hours to reach the target value. The mixture was then cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate represented by the following formula which was colorless transparent and solid.

[29]

Then, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene-type epoxy acrylate thus obtained, and then 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed , The temperature was gradually raised, and the reaction was carried out at 110 to 115 ° C for 4 hours. After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to obtain Resin A-1. The disappearance of the acid anhydride group was confirmed by IR spectrum.

[Example 1, Example 2, and Comparative Examples 1 to 3]

In Examples and Comparative Examples, a carboxy resin and a novolac resin were used as the alkali-soluble resin (A).

As the cardo resin, Resin A-1 obtained in Preparation Example 1 was used.

TO-547 (trade name) manufactured by Sumitomo Bakelite Co., Ltd. was used as the novolak resin. TO-547 is a cresol novolak resin having Mw of 30000 obtained by adding oxalic acid and a concentration of 37% by mass formalin to a mixture of 90 mol% of m-cresol and 10 mol% of 2,3,5-trimethylphenol and performing a condensation reaction by a conventional method.

In Examples and Comparative Examples, DPHA (dipentaerythritol hexaacrylate) was used as the photopolymerizable compound (B).

In Examples and Comparative Examples, OXE-02 (trade name, O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazole- - yl] ethanone oxime) was used.

In Examples and Comparative Examples, carbon black was used as the pigment (D).

As the carbon black, carbon black (pigment A (dispersion)) manufactured by Daido Chemical Industry Co., Ltd. was used.

In Table 1 of this embodiment, the numerical values of the sum of solid contents of the pigment and the dispersant are described.

In the examples and comparative examples, the following E1 to E3 were used as the silane coupling agent (E).

E1: Compound of the formula

[T]

E2: 3-glycidoxypropyltrimethoxysilane

E3: 3-phenylaminopropyltrimethoxysilane

(A), the photopolymerizable compound (B), the photopolymerization initiator (C), the pigment (D) and the kind and amount of the (E) epoxy compound Was dissolved and dispersed in an organic solvent (S) so as to have a solid concentration of 15% by mass to obtain resin compositions of each of Examples and Comparative Examples.

(S) A mixed solvent of 3-methoxybutyl acetate: propylene glycol monomethyl ether acetate: cyclohexanone = 40: 35: 25 (mass ratio) was used as the organic solvent.

Using the obtained resin composition, the adhesion of the patterned cured film to the substrate and the generation of the residue in the unexposed portion were evaluated according to the following methods. The evaluation results are shown in Table 1.

≪ Adhesion of the patterned cured film to the substrate >

The resin composition was coated on a glass substrate (100 mm x 100 mm) using a spin coater and prebaked at 80 캜 for 120 seconds to form a coating film having a thickness of 2.0 탆.

Subsequently, ultraviolet rays were irradiated onto the coating film through a mask for forming a line pattern having a line portion of the following width with an exposure gap of 250 mu m by using a mirror projection aligner (product name: TME-150RTO, did. The exposure dose was 40 mJ / cm ² .

The coated film after exposure was immersed in a 0.04 mass% KOH aqueous solution at 25 占 폚 for 60 seconds, and then a line pattern having a line size of 2 to 100 占 퐉 was formed, and the adhesion of the formed line pattern was evaluated according to the following criteria.

&Amp; cir &: Line patterns having a width of 2 mu m or less adhere closely.

?: A line pattern with a width of 3 to 5 占 퐉 was closely adhered.

?: A line pattern with a width of 6 to 10 占 퐉 is closely adhered.

X: Line pattern having a width of 11 mu m or more adhered closely.

≪ Occurrence of residue in unexposed portion >

The resin composition was coated on a glass substrate (100 mm x 100 mm) using a spin coater and prebaked at 80 캜 for 120 seconds to form a coating film having a thickness of 2.0 탆.

Subsequently, the coating film was irradiated with ultraviolet rays through a mask capable of forming a matrix having the following shape by using a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.) with an exposure gap of 250 μm. The exposure dose was 40 mJ / cm ² .

The coated film after exposure was immersed in a 0.04 mass% KOH aqueous solution at 25 占 폚 for 60 seconds, a matrix having a size of 11 占 퐉 was formed, and the number of residues to be identified in the matrix was measured. Based on the number of the measured residues, the occurrence of residue after development was evaluated according to the following criteria.

◎: 0 to 10 residues.

○: 11 to 20 residues.

Δ: 21 to 40 residues.

X: More than 41 residues.

(A) an alkali-soluble resin, a photopolymerizable compound (B), a photopolymerization initiator (C), a pigment (D) and a silane coupling agent (E) containing a compound having a predetermined structure It is possible to form a pattern with good adhesion to the substrate and to suppress the occurrence of development residue in the unexposed portion.

On the other hand, according to Comparative Examples 1 to 3, when the photosensitive resin composition does not contain the silane coupling agent (E) or when the silane coupling agent (E) does not contain the compound having the predetermined structure, It can be seen that it is difficult to achieve both of the formation of this good pattern and the suppression of the occurrence of development residue in the unexposed portion.

Claims (8)

The alkali-soluble resin (A)
The photopolymerizable compound (B)
A photopolymerization initiator (C)
The pigment (D)
Silane coupling agent (E)
, Wherein the resin composition
Wherein the silane coupling agent (E) is represented by the following formula (e1):
(R ^e1 ) _a (R ^e2 ) _3-a Si-R ^e3 -NH-CO-R ^e4 -R ^e5 (e1)
(In the formula (e1), R ^e1 and R ^e2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, a is 2 or 3, R ^e3 is an alkylene group having 1 to 10 carbon atoms, R ^e4 Is a bivalent organic group and R ^e5 is a Bronsted acid group, an alcoholic hydroxyl group, an amino group, or a carbamoyl group.)
Lt; RTI ID = 0.0 > (I) < / RTI > The method according to claim 1,
^Wherein R ^e4 is a divalent aromatic hydrocarbon group. The method of claim 2,
Wherein the relationship between the position of a carbon atom bonded to one bonding hand and the position of a carbon atom bonded to the other bonding hand in the bivalent aromatic hydrocarbon group is an adjacent position or a ferry position. The method of claim 3,
Wherein the bivalent aromatic hydrocarbon group is an o-phenylene group, a naphthalene-1,2-diyl group, a naphthalene-2,3-diyl group, or a naphthalene-1,8-diyl group. The method according to any one of claims 1 to 4,
And R ^e5 is a carboxyl group. A cured film obtained by curing the resin composition of any one of claims 1 to 5. A color filter comprising the cured film of claim 6. A step of forming a coating film by applying the resin composition of any one of claims 1 to 5,
Selectively exposing the coating film to light;
A step of developing the exposed coating film to form a patterned cured film,
And baking the patterned cured film.