KR102537532B1 - Resin Composition, Cured Film, Color Filter, and Preparing Method of Cured Film - Google Patents

Abstract

The present invention provides a resin composition capable of forming a pattern with good adhesion to a substrate and suppressing the generation of development residues in unexposed areas, a method for producing a cured film using the resin composition, and curing the resin composition. It is to provide a cured film formed by making and a color filter provided with the cured film.
To a resin composition containing an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a pigment (D), the following formula (e1):
(R ^e1 O _)a (R ^e2 ) _3-a Si-R ^e3 -NH-CO-R ^e4 -R ^e5 ... (e1)
(In 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, and R ^e4 is a divalent organic group, and R ^e5 is a Brensted acid group, an alcoholic hydroxyl group, an amino group, or a carbamoyl group.)
The compound represented by is blended as a silane coupling agent (E).

Description

Resin composition, cured film, color filter, and method for producing a cured film {Resin Composition, Cured Film, Color Filter, and Preparing Method of Cured Film}

The present invention relates to a resin composition, a cured film formed by curing the resin composition, a color filter provided with the cured film, and a method for producing a cured film using the above-described resin composition.

BACKGROUND OF THE INVENTION [0002] Display bodies such as liquid crystal displays have a structure in which a liquid crystal layer is sandwiched between two substrates on which electrodes forming pairs facing each other are formed. A color filter having pixels of each color such as red (R), green (G), and blue (B) is formed inside one substrate. In this color filter, in order to prevent color mixing of different colors in each pixel or to hide the pattern of electrodes, a black matrix arranged in a matrix form is formed to divide pixels of each color, usually R, G, and B. .

Generally, color filters are formed by lithography. Specifically, first, a black photosensitive composition is applied to a substrate, exposed to light, and developed to form a black matrix. After that, each color pattern is formed at a predetermined position by repeating application, exposure, and development for each photosensitive composition of each color of red (R), green (G), and blue (B) to form a color filter. .

A method of using a negative photosensitive resin composition has been proposed for a method of forming a colored film constituting a color filter, for example, a method of forming a black matrix.

For example, in Patent Document 1, as a black photosensitive resin composition serving as a raw material of a black matrix capable of achieving both high light-shielding properties and low reflectance at low cost, a negative photosensitive resin composition in which carbon black and hydrophobic silica fine particles are blended is has been initiated.

Japanese Unexamined Patent Publication No. 2015-161815

However, as a result of investigation by the present inventors, when using a conventional photosensitive resin composition such as the composition described in Patent Document 1, it is difficult to form a pattern that adheres well to the substrate, or residues are easily generated in unexposed areas. I found out that there are challenges.

The present invention has been made in view of the above problems, and provides a resin composition capable of forming a pattern with good adhesion to a substrate and suppressing the generation of development residues in unexposed areas, and a cured film using the resin composition. It aims at providing the manufacturing method, the cured film formed by hardening the said resin composition, and the color filter provided with the said cured film.

The present inventors added a compound having a specific structure to a resin composition containing an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a pigment (D) as a silane coupling agent (E) It was found that the above subject could be solved by blending as, and came to complete the present invention. Specifically, the present invention provides the following.

A first aspect of the present invention,

An alkali-soluble resin (A);

A photopolymerizable compound (B);

A photopolymerization initiator (C);

A pigment (D);

Silane Coupling Agent (E)

As a resin composition comprising a,

The silane coupling agent (E) has the following formula (e1):

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

(In formula (e1), R ^e1 and R ^e2 are Each independently represents a hydrocarbon group having 1 to 6 carbon atoms, a is 2 or 3, ^Re3 is an alkylene group having 1 to 10 carbon atoms, ^Re4 is a divalent organic group, and ^Re5 is a Brenstedt acidic group, alcoholic hydroxyl group, amino group, or carbamoyl group.)

It is a resin composition containing the alkoxysilane compound represented by.

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

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

A fourth aspect of the present invention includes the steps of forming a coating film by applying the resin composition related to the first aspect;

A step of positionally selectively exposing the coated film;

A step of developing the exposed coating film to form a patterned cured film;

It is a manufacturing method of a cured film including the process of baking a patterned cured film.

According to the present invention, a resin composition capable of forming a pattern having good adhesion to a substrate and suppressing the generation of development residue in unexposed areas, a method for producing a cured film using the resin composition, and the resin composition A cured film formed by curing and a color filter provided with the cured film can be provided.

Hereinafter, the present invention will be described based on preferred embodiments. In addition, "-" in this specification represents the following (upper limit value) from the above (lower limit value) unless there is particular notice.

<<resin composition>>

The resin composition contains 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 formula (e1):

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

(In 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, and R ^e4 is a divalent organic group, and R ^e5 is a Brensted acid group, an alcoholic hydroxyl group, an amino group, or a carbamoyl group.)

It includes an alkoxysilane compound represented by

In the present embodiment, the resin composition can form a pattern with good adhesion to the substrate by containing the above silane coupling agent (E), and can suppress the generation of development residue in the unexposed area. is obtained

Hereinafter, essential or optional components contained in the resin composition and methods for preparing the resin composition are described.

<Alkali-soluble resin (A)>

The resin composition contains an alkali-soluble resin (A) (also described as "component (A)" in this specification). It does not specifically limit as alkali-soluble resin (A), It can select suitably from the alkali-soluble resin conventionally mix|blended with various photosensitive resin compositions.

In this 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.) that imparts alkali solubility in the molecule.

Resin (A1) which has a cardo structure (hereinafter also described as "cardo resin (A1)") is mentioned as resin suitable as alkali-soluble resin.

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

[Resin (A1) having a cardo structure]

As the resin (A1) having a cardo structure, a resin having a cardo skeleton in its structure and having a predetermined alkali solubility can be used. The cardo skeleton refers to a skeleton in which the second cyclic structure and the third cyclic structure are bonded to one ring carbon atom constituting the first cyclic structure. In addition, the 2nd annular structure and the 3rd annular structure may be the same structure or different structures may be sufficient as them.

A representative 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 9th position of the fluorene ring.

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

[Tue 1]

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

[Tue 2]

In the formula (a-2), R ^a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ^a2 each independently represents a hydrogen atom or a methyl group, and R ^a3 is Each 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).

[Tue 3]

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

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

Examples of the aliphatic ring include monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes.

Specifically, monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane are exemplified.

An aromatic hydrocarbon ring or an aromatic heterocyclic ring may be sufficient as the aromatic ring which may be condensed with an aliphatic ring, and an aromatic hydrocarbon ring is preferable. Specifically, a benzene ring and a naphthalene ring are preferable.

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

[Tuesday 4]

Divalent group ^{X a} in formula (a-1) is introduced into cardo resin (A1) by reacting tetracarboxylic dianhydride giving residue Z ^a with a diol compound represented by formula (a-2a) below.

[Tuesday 5]

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

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

First, after replacing the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) with a group represented by -R ^a3 -OH according to a conventional method as necessary, epichlorohydrin etc. It glycidylates using, and obtains the epoxy compound represented by the following formula (a-2c).

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

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

In addition, the manufacturing method of the diol compound represented by formula (a-2a) is not limited to said method.

[Tue 6]

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

[Tue 7]

In the formula (a-1), R ^a0 is a hydrogen atom or a group represented by -CO-Y ^a -COOH. Here, Y ^a represents a residue obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-endo-methylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, Anhydrous glutaric acid etc. are mentioned.

Moreover, in said formula (a-1), Z ^<a> represents the residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride represented by the following formula (a-4). can be heard

Moreover, in said formula (a-1), m represents the integer of 0-20.

[Tue 8]

(In formula (a-4), each of R ^a4 , R ^a5 , and R ^a6 independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and m3 is 0 to 10 Represents an integer of 12.)

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

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

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

A plurality of R ^a4 in formula (a-4) is preferably the same group from the viewpoint of easy preparation of high-purity tetracarboxylic dianhydride.

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

From the viewpoint of easy purification of tetracarboxylic dianhydride, 5 is preferable and, as for the upper limit of m3, 3 is more preferable.

From the point of chemical stability of tetracarboxylic dianhydride, as for the lower limit of m3, 1 is preferable and 2 is more preferable.

As for m3 in Formula (a-4), 2 or 3 is especially preferable.

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

R ^a5 and R ^a6 are hydrogen atoms or 1 to 10 carbon atoms (preferably 1 to 6, more preferably 1 to 5, still more preferably 1, from the viewpoint of easy purification of tetracarboxylic dianhydride). It is preferable that it is an alkyl group of -4, especially preferably 1-3), and it is especially preferable that it is a hydrogen atom or a methyl group.

As tetracarboxylic dianhydride represented by formula (a-4), for example, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'' ,6,6''-tetracarboxylic dianhydride (aka "norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-norbornane-5,5'',6, 6''-tetracarboxylic dianhydride"), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-(methylnorbornane)-5,5'',6, 6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid dianhydride (aka "norbornane-2-spiro-2'-cyclohexanone-6'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride" ), methylnorbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-(methylnorbornane)-5,5'',6,6''-tetracarboxylic dianhydride, Norbornane-2-spiro-α-cyclopropanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2- Spiro-α-cyclobutanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclohep Tanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclooctanone-α'-spiro -2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclononanone-α'-spiro-2''-nor Bornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclodecanone-α'-spiro-2''-norbornane-5,5 '',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanone-α'-spiro-2''-norbornane-5,5'',6,6 ''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid 2 Anhydride, norbornane-2-spiro-α-cyclotridecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane -2-spiro-α-cyclotetradecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro- α-Cyclopentadecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclo Pentanone) -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.

(A1) The weight average molecular weight of cardo resin is preferably 1000 to 40000, more preferably 1500 to 30000, still more preferably 2000 to 10000. By setting it as said range, sufficient heat resistance and film strength can be obtained, obtaining favorable developability.

[Acrylic Resin (A2)]

Alkali-soluble resin (A) may contain alkali-soluble resin other than cardo resin (A1). Acrylic resin (A2) is mentioned as such an alkali-soluble resin.

As the acrylic resin (A2), one containing a structural unit derived from (meth)acrylic acid and/or a structural unit derived from other monomers such as (meth)acrylic acid ester can be used. (Meth)acrylic acid is acrylic acid or methacrylic acid. The (meth)acrylic acid ester is represented by the following formula (a-5) and is not particularly limited as long as the object of the present invention is not impaired.

[Tue 9]

In the formula (a-5), R ^a7 is a hydrogen atom or a methyl group, and R ^a8 is a monovalent organic group. This organic group may contain a bond other than a hydrocarbon group such as a hetero atom or a substituent in the above organic group. Moreover, either linear, branched chain, or cyclic may be sufficient as this organic group.

Substituents other than a 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 a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an iso Cyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, a A real group, an acyloxy group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, a hydroxyimino group, an alkyl ether group, an alkylthio ether group, an aryl ether group, an arylthioether group, an amino group (-NH ₂ , -NHR, -NRR': R and R' each independently represent a hydrocarbon group), and the like. The hydrogen atom contained in the said substituent may be substituted by the hydrocarbon group. Moreover, any of linear, branched chain, and cyclic may be sufficient as the hydrocarbon group contained in the said substituent.

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

As for the number of carbon atoms, when an alkyl group is a linear or branched thing, 1-20 are preferable, 1-15 are more preferable, and 1-10 are especially preferable. Examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group etc. can be mentioned.

When the alkyl group is an alicyclic group or a group containing an alicyclic group, suitable alicyclic groups included in the alkyl group include monocyclic alicyclic groups such as a cyclopentyl group and a cyclohexyl group, an adamantyl group, a norbornyl group, an isobornyl group, Polycyclic alicyclic groups, such as a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group, are mentioned.

Moreover, (A2) acrylic resin may be what polymerized monomers other than (meth)acrylic acid ester. Examples of such monomers include (meth)acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, and styrenes. These monomers can be used alone or in combination of two or more.

As (meth)acrylamides, (meth)acrylamide, N-alkyl (meth)acrylamide, N-aryl (meth)acrylamide, N,N-dialkyl (meth)acrylamide, N,N-aryl (meth)acrylamide ) Acrylamide, N-methyl-N-phenyl (meth)acrylamide, N-hydroxyethyl-N-methyl (meth)acrylamide, etc. are mentioned.

Examples of 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; etc. can be mentioned.

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; etc. can be mentioned.

As vinyl ethers, 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, tetrahydrofurfuryl vinyl ether, etc. Alkyl vinyl ether of; 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; etc. can be mentioned.

Vinyl esters include vinyl butylate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, and vinyl phenyl. Acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

Examples of styrene include styrene; Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene Alkyl styrene, such as acetoxymethyl styrene; Alkoxy styrene, such as methoxy styrene, 4-methoxy-3-methyl styrene, and dimethoxy styrene; Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl Halo styrene, such as styrene and 4-fluoro-3-trifluoromethyl styrene; etc. can be mentioned.

The amount of structural units derived from (meth)acrylic acid and the amount of structural units derived from other monomers in the acrylic resin (A2) are not particularly limited as long as the object of the present invention is not impaired. 5-50 mass % is preferable with respect to the mass of acrylic resin, and, as for the quantity of the structural unit derived from (meth)acrylic acid in acrylic resin (A2), 10-30 mass % is more preferable.

It is preferable that it is 2000-50000, and, as for the weight average molecular weight of acrylic resin (A2), it is more preferable that it is 5000-30000. By setting it as the said range, there exists a tendency for it to be easy to balance the film-forming ability of a resin composition and the developability after exposure.

[Novolac resin (A3)]

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

As the novolak resin (A3), various novolac resins that have conventionally been blended in photosensitive resin compositions can be used. As the novolak resin (A3), one obtained by subjecting an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") and an aldehyde to addition condensation under an acid catalyst is preferable.

(phenols)

Examples of the phenols used when producing the novolak resin (A3) include phenol; Cresols, such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, etc. silenols; ethyl phenols such as o-ethyl phenol, m-ethyl phenol, and p-ethyl phenol; alkyl phenols such as 2-isopropyl phenol, 3-isopropyl phenol, 4-isopropyl phenol, o-butyl phenol, m-butyl phenol, p-butyl phenol, and p-tert-butyl phenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglycinol; alkyl polyhydric phenols such as alkylresorcines, alkylcatechols, and alkylhydroquinones (each alkyl group has 1 to 4 carbon atoms); α-naphthol; β-naphthol; hydroxydiphenyl; and bisphenol A; and the like. 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 adjusted by adjusting the mixing ratio of both.

Although the blending ratio of m-cresol and p-cresol is not particularly limited, the molar ratio of m-cresol/p-cresol is preferably 3/7 or more and 8/2 or less. By using m-cresol and p-cresol in a ratio within these ranges, it is easy to obtain a resin composition capable of forming a cured film having excellent heat resistance.

Moreover, the novolac resin manufactured by using m-cresol and 2,3,5-trimethylphenol together is also preferable. In the case of using such a novolak resin, it is particularly easy to obtain a resin composition capable of forming a cured film that is difficult to excessively flow by heating at the time of post-baking.

Although the blending ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited, the molar ratio of m-cresol/2,3,5-trimethylphenol is preferably 70/30 or more and 95/5 or less.

(aldehydes)

Examples of aldehydes used when producing the novolac resin (A3) include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used independently or may be used in combination of 2 or more types.

(acid catalyst)

As an acid catalyst used when manufacturing novolac resin (A3), For example, 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 p-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; hereinafter also simply referred to as "weight average molecular weight") of the novolac resin (A3) in terms of polystyrene is the lower limit from the viewpoint of resistance to flow caused by heating of a cured film formed using a resin composition. 2000 is preferable, 5000 is more preferable, 10000 is particularly preferable, 15000 is more preferable, 20000 is most preferable, and the upper limit is preferably 50000, more preferably 45000, still more preferably 40000, and 35000 this is most preferable

As the novolak resin (A3), at least two types of resins having different weight average molecular weights in terms of polystyrene can be used in combination. By using those having different weight average molecular weights in a large or small combination, it is possible to balance the developability of the resin composition and the heat resistance of a cured film formed using the resin composition.

It is preferable that it is 10-65 mass % with respect to the mass of the whole solid content of a resin composition, and, as for content of alkali-soluble resin (A), it is more preferable that it is 15-50 mass %. By setting it as said range, it is easy to obtain the resin composition excellent in developability.

When using Cardo resin (A1), the content thereof is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and more preferably 15 to 30% by mass, based on the total mass of the solid content of the resin composition. more preferable By setting it as said range, it is possible to form a cured film that is more difficult to flow excessively by heating at the time of post-baking, and it is easy to obtain a resin composition excellent in developability.

When using acrylic resin (A2), its content is preferably 2 to 55% by mass, more preferably 4 to 50% by mass, and still more preferably 8 to 45% by mass with respect to the total mass of the solid content of the resin composition. desirable. By setting it as said range, it is easy to obtain the resin composition which can form the cured film which does not flow excessively by heating at the time of post-baking, and which is excellent in developability.

When using novolac resin (A3), its content is preferably 0.2 to 15% by mass, more preferably 0.5 to 10% by mass, and preferably 0.8 to 5% by mass with respect to the total mass of the solid content of the resin composition. more preferable By setting it as said range, it is easy to obtain the resin composition which can form the cured film which does not flow excessively by heating at the time of post-baking, and which is excellent in developability.

<Photopolymerizable compound (B)>

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

Monofunctional monomers include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, and butoxymethoxymethyl. (meth)acrylamide, N-methylol(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citracone acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2 -Ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropylphthalate, 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) Acrylates, half (meth)acrylates of phthalic acid derivatives, and the like are exemplified. These monofunctional monomers can be used alone or in combination of two or more.

On the other hand, as the multifunctional monomer, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ) Acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di ( 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 hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxy Diethoxyphenyl) propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol di Glycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether Poly(meth)acrylate, urethane(meth)acrylate (i.e., a reaction product of tolylene diisocyanate, trimethylhexamethylene diisocyanate, or hexamethylene diisocyanate with 2-hydroxyethyl(meth)acrylate), methylenebis(meth)acrylate ) polyfunctional monomers such as acrylamide, (meth)acrylamide methylene ether, and condensates of polyhydric alcohols and N-methylol (meth)acrylamide; triacryl formal; and the like. These polyfunctional monomers can be used alone or in combination of two or more.

Among the monomers having an ethylenically unsaturated group, a trifunctional or higher functional polyfunctional monomer is preferred, and a tetrafunctional or higher functional polyfunctional monomer is more preferred from the viewpoint of tending to increase the adhesion of the resin composition to the substrate and the strength after curing of the resin composition. And, a polyfunctional monomer having 5 or more functional groups is more preferred.

Specifically, a pentafunctional or higher functional polyfunctional monomer is preferably used, and it is more preferable that dipentaerythritol penta(meth)acrylate and/or dipentaerythritol hexa(meth)acrylate be used.

The content of the photopolymerizable compound (B) in the resin composition is preferably from 1 to 50% by mass, more preferably from 5 to 40% by mass, based on the total mass of the solid content of the resin composition. By setting it as the said range, there exists a tendency to balance sensitivity, developability, and resolution easily.

<Photoinitiator (C)>

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

As the photopolymerization initiator (C), specifically, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl ]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecyl Phenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, O -Acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, (9-ethyl-6-nitro-9H-carbazol-3-yl) [4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetyloxime, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octane one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Butyl dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethylacetal, benzyldimethylketal, 1-phenyl-1,2-propanedione -2-(O-ethoxycarbonyl)oxime, o-benzoylmethylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4 -Propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octaquinone Methylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzoimidazole, 2-mercaptobenzo Oxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone , p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroaceto Phenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosberone, pentyl-4-dimethylaminobenzoate, 9- Phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2- (5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6- Bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2- [2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloro) Methyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6 -bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-triclo Romethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl- s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, and the like. These photoinitiators can be used alone or in combination of two or more.

Among these, it is particularly preferable from the viewpoint of sensitivity to use an oxime-based photopolymerization initiator. Among the oxime photopolymerization initiators, particularly preferred are O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, ethanone, and 1-[ 9-ethyl-6-(pyrrole-2-ylcarbonyl)-9H-carbazol-3-yl],1-(O-acetyloxime), and 2-(benzoyloxyimino)-1-[4-( phenylthio)phenyl]-1-octanone.

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

[Tue 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 from 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 formula (c1), R ^c1 is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Preferred examples when 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 phenoxy group which may have a substituent, Benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, 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 which may have a substituent, a heterocyclyl group which may have a substituent, an amino group, amino group, morpholin-1-yl group, and piperazin-1-yl group substituted with 1 or 2 organic groups, halogen, nitro group, cyano group, and the like. When n1 is an integer of 2 to 4, R ^c1 may be the same or different. Moreover, the number of carbon atoms of the substituent which a substituent further has is not included in the number of carbon atoms of a substituent.

When R ^<c1> is an alkyl group, 1-20 carbon atoms are preferable and 1-6 carbon atoms are more preferable. Moreover, when R ^<c1> is an alkyl group, it may be straight-chain or branched-chain. Specific examples when R ^c1 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group A real group, an isodecyl group, etc. are mentioned. Moreover, when ^Rc1 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 methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

When R ^<c1> is an alkoxy group, 1-20 carbon atoms are preferable and 1-6 carbon atoms are more preferable. Moreover, when R ^<c1> is an alkoxy group, it may be straight-chain or branched-chain. Specific examples in case R ^c1 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, etc. are mentioned. Moreover, when R ^<c1> is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a 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 propyloxyethoxyethoxy group, and a methoxy group. A propyloxy group etc. are mentioned.

When R ^<c1> is a cycloalkyl group or a cycloalkoxy group, 3-10 carbon atoms are preferable and 3-6 carbon atoms are more preferable. A cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group etc. are mentioned as a specific example in case R ^<c1> is a cycloalkyl group. Specific examples in case R ^c1 is a cycloalkoxy group include cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, and cyclooctyloxy group.

When R ^<c1> is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, 2-20 carbon atoms are preferable and 2-7 carbon atoms are more preferable. Specific examples of when R ^c1 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexanoyl group, n -Heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentanoyl group A decanoyl group, and an n-hexadecanoyl group, etc. are mentioned. Specific examples in case R ^c1 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, and 2,2-dimethylpropanoyloxy group. , n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n- Tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

When R ^<c1> is an alkoxycarbonyl group, 2-20 carbon atoms are preferable and 2-7 carbon atoms are more preferable. Specific examples of when R ^c1 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxy group. carbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec- Octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group, etc. are mentioned.

When R ^<c1> is a phenylalkyl group, 7-20 carbon atoms are preferable and 7-10 carbon atoms are more preferable. Moreover, when R ^<c1> is a naphthylalkyl group, 11-20 carbon atoms are preferable and 11-14 carbon atoms are more preferable. Specific examples in 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 in case R ^c1 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-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 naphthyl group.

When R ^c1 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more of N, S, and O, or a heterocyclyl group formed by condensation of such monocycles or a benzene ring. When the heterocyclyl group is a condensed ring, it is assumed that the ring number is up to 3. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, and pyrimidine. , pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthala gin, cinoline, and quinoxaline; and the like. 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, 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, and 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, C11-C20 naphthylalkyl group which may have a substituent, heterocyclyl group, etc. are mentioned. Specific 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 methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, and di-n-butylamino group. , n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoyl amino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group; can

Examples of substituents in the case where the phenyl group, naphthyl group, and heterocyclyl group in R ^c1 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a substituent 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 Dialkylamino group, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, and cyano group having When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c1 further have substituents, the number of substituents is not limited to the range not impairing the object of the present invention, but is preferably 1 to 4. When the phenyl group, naphthyl group, and heterocyclyl group contained in ^Rc1 have a plurality of substituents, the plurality of substituents may be the same or different.

In R ^c1 , it is chemically stable, has little steric hindrance, and is easy to synthesize an oxime ester compound, such as an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an oxime ester compound having 2 carbon atoms. A group selected from the group consisting of a saturated aliphatic acyl group of ∼7 is preferred, an alkyl having 1 to 6 carbon atoms is more preferred, and a methyl group is particularly preferred.

The position at which R ^c1 is bonded to the phenyl group is at position 4, when the position of ^the bond hand of the main skeleton of the phenyl group and the oxime ester compound is set to position 1 and the position of the methyl group is set to position 2, relative to the phenyl group to which R c1 is bonded. , or the 5th position is preferred, and the 5th position is more preferred. Moreover, 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. Moreover, when ^Rc2 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 of the phenyl group or the carbazolyl group is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that the phenyl group or the carbazolyl group may have on the carbon atom include an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, and a carbon atom. A cycloalkoxy group of 3 to 10 atoms, a saturated aliphatic acyl group of 2 to 20 carbon atoms, an alkoxycarbonyl group of 2 to 20 carbon atoms, a saturated aliphatic acyloxy group of 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, carbon which may have a substituent Phenylalkyl group having 7 to 20 atoms, naphthyl group which may have a substituent, naphthoxy group which may have a substituent, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthyl which may have a substituent Substituted with a toyloxy group, 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, or 1 or 2 organic groups amino group, morpholin-1-yl group, and piperazin-1-yl group, halogen, nitro group, and cyano group, and the like.

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 of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, and a cycloalkyl group of 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, and a substituent which may have 7 to 20 carbon atoms A phenylalkyl group, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, even if it has a substituent The heterocyclyl group which becomes it, and the heterocyclyl carbonyl group which may have a substituent, etc. are mentioned. Among these substituents, an alkyl group of 1 to 20 carbon atoms is preferable, an alkyl group of 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

About the specific example of the substituent which a phenyl group or a carbazolyl group may have, 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, the phenylalkyl group which may have a substituent , a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and an amino group substituted with 1 or 2 organic groups, the same as ^Rc1 .

In R ^c2 , examples of the substituent in case the phenyl group, naphthyl group, and heterocyclyl group included in the substituent 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; alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group; naphthoyl group; a benzoyl group substituted with 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 having 1 to 6 carbon atoms; dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholine-1-yl group; piperazine-1-yl group; halogen; nitro group; A cyano group is mentioned. When the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituents of the phenyl group or the carbazolyl group further have substituents, the number of the substituents is not limited within the range that does not impair the object of the present invention, but is 1 to 4 is preferred. 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.

In R ^c2 , from the viewpoint of obtaining a photopolymerization initiator with excellent sensitivity, a group represented by the following formula (c2) or (c3) is preferred, and a group represented by the following formula (c2) is more preferred, and the following formula (c2) As the group represented by , a group in which A is S is particularly preferred.

[Tue 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.)

[Tue 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 various organic groups within a range not impairing the object of the present invention. Preferred examples in the case where R ^c4 in the formula (c2) is an organic group 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; alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group; naphthoyl group; a benzoyl group substituted with 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 having 1 to 6 carbon atoms; dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholine-1-yl group; piperazine-1-yl group; halogen; nitro group; A cyano group is mentioned.

Among R ^c4 , a benzoyl group; naphthoyl group; a benzoyl group substituted with 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, and a benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4-(piperazin-1-yl)phenylcarbonyl group; A 4-(phenyl)phenylcarbonyl group is more preferred.

In 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. When n3 is 1, the position at which R ^c4 is bonded is preferably para-position with respect to the bond at which the phenyl group to which R ^c4 is bonded is bonded to an oxygen atom or a sulfur atom.

R ^c5 in formula (c3) can be selected from various organic groups within a range not impairing the object of the present invention. Preferred examples of R ^c5 include an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, a saturated aliphatic acyl group of 2 to 20 carbon atoms, an alkoxycarbonyl group of 2 to 20 carbon atoms, and a substituent. 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, and a naphtho which may have a substituent 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; can

Among R ^c5 , an alkyl group of 1 to 20 carbon atoms is preferable, an alkyl group of 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

R ^c6 in the formula (c3) is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Specific examples of groups suitable for 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 ^Rc6 , among these groups, a phenyl group which may have a substituent is more preferable, and a 2-methylphenyl group is particularly preferable.

Examples of substituents in the case where the phenyl group, naphthyl group, and heterocyclyl group in R ^c4 , R ^c5 , or R ^c6 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A monoalkylamino group having 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, an alkyl group having 1 to 6 carbon atoms, carbon A dialkylamino group having an alkyl group of 1 to 6 atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group, and the like. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c4 , R ^c5 , or R ^c6 further have substituents, the number of the substituents is not limited to the range not impairing the object of the present invention, but is 1 to 10 4 is preferred. When the phenyl group, naphthyl group, and 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 formula (c1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. As ^Rc3 , 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), PI-1 to PI-42 shown below are exemplified as particularly suitable compounds.

[Tue 13]

[Tue 14]

[Tuesday 15]

[Tue 16]

[Tue 17]

[Tue 18]

Moreover, the oxime ester compound represented by following formula (c4) is also preferable as a photoinitiator.

[Tue 19]

(R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group, R ^c8 and R ^c9 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, and R ^c8 and R ^c9 may combine with each other to form a ring, R ^c10 is a monovalent organic group, 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, n4 is an integer from 0 to 4, and n5 is 0 or 1.)

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

[Tue 20]

(R ^c7 , R ^c8 , R ^c9 , R ^c10 , n4, and n5 are as shown in Formula (c4).)

In formulas (c4) and (c5), R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group. R ^c7 bonds to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by -(CO) _n5- on the fluorene ring in formula (c4). In formula (c4), the bonding position of R ^c7 to the fluorene ring is not particularly limited. When the compound represented by formula (c4) has one or more R ^c7 , the synthesis of the compound represented by formula (c4) is easy, so that one of the one or more R ^c7 bonds to the 2-position of the fluorene ring. it is desirable When there are plural R ^c7 , the plural R ^c7 may be the same or different.

When R ^c7 is an organic group, R ^c7 is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Preferred examples when R ^c7 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 phenoxy group which may have a substituent, Benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, naphthoxy group which may have a substituent , naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, substituent The heterocyclylcarbonyl group which may have, the amino group substituted with 1 or 2 organic groups, the morpholin-1-yl group, the piperazin-1-yl group, etc. are mentioned.

As for the number of carbon atoms of an alkyl group, when ^Rc7 is an alkyl group, 1-20 are preferable and 1-6 are more preferable. Moreover, when ^Rc7 is an alkyl group, it may be straight-chain or branched-chain. Specific examples when R ^c7 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group A real group, an isodecyl group, etc. are mentioned. Moreover, when ^Rc7 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 methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

As for the number of carbon atoms of an alkoxy group, when ^Rc7 is an alkoxy group, 1-20 are preferable and 1-6 are more preferable. Moreover, when ^Rc7 is an alkoxy group, it may be straight-chain or branched-chain. Specific examples in case R ^c7 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, etc. are mentioned. In addition, 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 propyloxyethoxyethoxy group, and a methoxy group. A propyloxy group etc. are mentioned.

As for the number of carbon atoms of a cycloalkyl group or a cycloalkoxy group, when R ^<c7> is a cycloalkyl group or a cycloalkoxy group, 3-10 are preferable and 3-6 are more preferable. A cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group etc. are mentioned as a specific example in case ^Rc7 is a cycloalkyl group. A cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group etc. are mentioned as a specific example in case ^Rc7 is a cycloalkoxy group.

As for the carbon atom number of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, when ^Rc7 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, 2-21 are preferable and 2-7 are more preferable. Specific examples of when R ^c7 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexanoyl group, n -Heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentanoyl group A decanoyl group, and an n-hexadecanoyl group, etc. are mentioned. Specific examples when R ^c7 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, and 2,2-dimethylpropanoyloxy group. , n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n- Tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

As for the number of carbon atoms of an alkoxycarbonyl group, when ^Rc7 is an alkoxycarbonyl group, 2-20 are preferable and 2-7 are more preferable. Specific examples of when R ^c7 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxy group. carbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec- Octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group, etc. are mentioned.

When R ^c7 is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 to 20, more preferably 7 to 10. Moreover, as for the number of carbon atoms of a naphthylalkyl group, when ^Rc7 is a naphthylalkyl group, 11-20 are preferable and 11-14 are more preferable. Specific examples in case 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 in case R ^c7 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-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 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 of N, S, and O, or a heterocyclyl group formed by condensation of such monocycles or a benzene ring. When the heterocyclyl group is a condensed ring, it is assumed that the ring number is up to 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, and pyrimidine. , pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthala gin, chinoline, quinoxaline, piperidine, piperazine, morpholine, tetrahydropyran, and tetrahydrofuran; and the like. 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 an organic group of 1 or 2, suitable examples of the organic group include an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, and a saturated aliphatic group of 2 to 21 carbon atoms. A phenyl group which may have a real group, 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 substituent A naphthylalkyl group having 11 to 20 carbon atoms which may have, and a heterocyclyl group. Specific examples of these suitable organic groups are the same as R ^c7 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, and di-n-butylamino group. , n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoyl amino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group; can

Examples of substituents in the case where the phenyl group, naphthyl group, and heterocyclyl group in R ^c7 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a substituent 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 Dialkylamino group, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, and cyano group having When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c7 further have substituents, the number of substituents is not limited to the range not impairing the object of the present invention, but is preferably 1 to 4. When the phenyl group, naphthyl group, and heterocyclyl group contained in ^Rc7 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, a nitro group or a group represented by R ^c12 -CO- as R ^c7 is preferable because 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 can be selected from various organic groups. Examples of groups suitable for 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. Among these groups as R ^c12 , a 2-methylphenyl group, a thiophen-2-yl group, and an α-naphthyl group are particularly preferred.

In addition, when R ^c7 is a hydrogen atom, transparency tends to be improved, and is preferable. Transparency tends to be better when R ^c7 is a hydrogen atom and R ^c10 is a group represented by formula (c4a) or (c4b) described later.

In formula (c4), each of R ^c8 and R ^c9 is a 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 combine with each other to form a ring. Among these groups, chain alkyl groups which may have substituents are preferred as R ^c8 and R ^c9 . When ^Rc8 and ^Rc9 are a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ^c8 and R ^c9 are chain alkyl groups having no substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 6. Specific examples when R ^c8 and R ^c9 are chain alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group , n-decyl group, and isodecyl group. Moreover, when ^Rc8 and ^Rc9 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 methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

When R ^c8 and R ^c9 are chain alkyl groups having a substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In this case, the number of carbon atoms in the substituent is not included in the number of carbon atoms in the chain alkyl group. It is preferable that the chain|chain alkyl group which has a substituent is linear.

Substituents that the alkyl group may have are not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. As a cyclic organic group, a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group are mentioned. As a specific example of a cycloalkyl group, it is the same as a suitable example in case ^Rc7 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 linear or branched, preferably linear. 1-10 are preferable and, as for the number of carbon atoms of the alkoxy group contained in an alkoxycarbonyl group, 1-6 are more preferable.

When the chain alkyl group has a substituent, the number of substituents is not particularly limited. The number of preferred substituents varies depending on the number of carbon atoms in 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. As a cyclic organic group, an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group are mentioned. When ^Rc8 and ^Rc9 are cyclic organic groups, the substituents that the cyclic organic groups may have are the same as those in the case where ^Rc8 and ^Rc9 are chain alkyl groups.

When R ^c8 and R ^c9 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by bonding a plurality of benzene rings via a carbon-carbon bond, or a group formed by condensation of a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensation of a plurality of benzene rings, the number of rings of the benzene rings contained in the aromatic hydrocarbon group is not particularly limited, preferably 3 or less, more preferably 2 or less, and especially 1 desirable. Preferable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

When ^Rc8 and ^Rc9 are an aliphatic cyclic hydrocarbon group, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20 and 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 isobornyl group, a tricyclononyl group, a tricyclodecyl group, A tetracyclododecyl group, an adamantyl group, etc. are mentioned.

When R ^c8 and R ^c9 are heterocyclyl groups, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing at least one N, S, and O, or a heterocyclyl condensed between these monocycles or such monocycles and a benzene ring. It is Ki. When the heterocyclyl group is a condensed ring, it is assumed that the ring number is up to 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, and pyrimidine. , pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthala gin, chinoline, quinoxaline, piperidine, piperazine, morpholine, tetrahydropyran, and tetrahydrofuran; and the like.

R ^c8 and R ^c9 may combine with each other to form a ring. It is preferable that the group consisting of the ring formed by ^Rc8 and ^Rc9 is a cycloalkylidene group. When ^Rc8 and ^Rc9 combine 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 ^Rc8 and ^Rc9 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of rings that 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, a pyridine ring, and a pyraline ring. A true ring, and a pyrimidine ring, etc. are mentioned.

Examples of suitable groups among R ^c8 and R ^c9 described above 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.

1-10 are preferable and, as for carbon atoms of the linear alkylene group of A ^<1> , 1-6 are more preferable. When A ² is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. 1-10 are preferable and, as for the number of carbon atoms of an alkoxy group, 1-6 are more preferable. 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, chlorine atom, bromine atom or iodine atom, and more preferably a fluorine atom, chlorine atom or bromine atom. The halogenated alkyl group may be linear or branched, and is preferably linear. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic groups that R ^c8 and R ^c9 have as substituents. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups that ^Rc8 and ^Rc9 have as substituents.

Preferable specific 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; 2-methoxyethyl group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy -n-heptyl group, 8-methoxy-n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-phen alkoxyalkyl groups such as ethyl group, 6-ethoxy-n-hexyl group, 7-ethoxy-n-heptyl group, and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano-n-hexyl group, 7-cyano group -cyanoalkyl groups such as n-heptyl group and 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and phenylalkyl groups such as 8-phenyl-n-octyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl -n-heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-phen Cycloalkylalkyl groups such as ethyl group, 6-cyclopentyl-n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-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-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n-heptyl group, and 8 -alkoxycarbonylalkyl groups such as ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo- n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5, Halogenated alkyl groups, such as a 5-heptafluoro-n-pentyl group, are mentioned.

Suitable groups among the above as R ^c8 and R ^c9 are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-heptafluoro- It is an n-pentyl group.

Examples of suitable organic groups for R ^c10 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 phenyl group which may have a substituent, and a substituent, as in R ^c7 . A phenoxy 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 which may have a substituent, a naphthyl group which may have a substituent, a substituent naphthoxy group which may have a substituent, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, hetero group which may have a substituent A krill group, a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group. Specific examples of these groups are as described for R ^c7 . Moreover, as ^Rc10 , a cycloalkylalkyl group, the phenoxyalkyl group which may have a substituent on the aromatic ring, and the phenylthioalkyl group which may have a substituent on the aromatic ring are preferable. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group in ^Rc7 may have.

Among organic groups, as ^Rc10 , an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, and a phenylthioalkyl group which may have a substituent on the aromatic ring are preferable. The alkyl group is preferably an alkyl group of 1 to 20 carbon atoms, more preferably an alkyl group of 1 to 8 carbon atoms, particularly preferably an alkyl group of 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. 5-10 are preferable, as for the number of carbon atoms of the cycloalkyl group contained in a cycloalkylalkyl group, 5-8 are more preferable, and 5 or 6 are especially preferable. The number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. As for the carbon atom number of the alkylene group contained in the phenylthioalkyl group which may have a substituent on an aromatic ring, 1-8 are preferable, 1-4 are more preferable, and 2 is especially preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2-(4-chlorophenylthio)ethyl group is preferable.

Moreover, as ^Rc10 , group represented by -A ³ -CO-OA ⁴ is also preferable. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ⁴ is a monovalent organic group, preferably a monovalent hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be linear or branched, preferably linear. As for the number of carbon atoms of an alkylene group, when A ^<3> is an alkylene group, 1-10 are preferable, 1-6 are more preferable, and 1-4 are especially preferable.

Preferable 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. Preferable specific examples of A ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, α-naphthylmethyl group, and β-naphthylmethyl group; and the like.

Preferred specific examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propyloxycarbonylethyl, and 2-n-butyloxycarbonyl. Ethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group , 3-ethoxycarbonyl-n-propyl group, 3-n-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, etc. are mentioned.

As mentioned above, although R ^c10 was demonstrated, as R ^c10 , the group represented by the following formula (c4a) or (c4b) is preferable.

[Tue 21]

(In 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 may combine with each other to form a ring, n7 is an integer of 1 to 8, n8 is an integer of 1 to 5, n9 is an integer of 0 to (n8 + 3), R ^c15 is an organic group.)

Examples of organic groups for R ^c13 and R ^c14 in formula (c4a) are 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 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R ^c13 is most preferably a methyl group. When ^Rc13 and ^Rc14 combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. Suitable examples of the group represented by formula (c4a), in which ^Rc13 and ^Rc14 form a ring, include naphthalen-1-yl group, 1,2,3,4-tetrahydronaphthalen-5-yl group, and the like. can 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. Examples of the organic group include the same groups as those described for ^Rc7 . Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. 1-10 are preferable, as for the number of carbon atoms of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. As ^Rc15 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. are exemplified preferably, 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, and 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, 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 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 a substituent which may have when ^Rc11 is an alkyl group, a phenyl group, a naphthyl group, etc. are illustrated preferably. Moreover, as a substituent which may have when ^Rc7 is an aryl group, a C1-C5 alkyl group, an alkoxy group, a halogen atom, etc. are illustrated preferably.

In formula (c4), preferred examples of R ^c11 include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group, and the like. Among these, A methyl group or a phenyl group is more preferred.

The compound represented by formula (c4) is a step of converting the oxime group (>C=N-OH) contained in the compound represented by formula (c5) described above to an oxime ester group represented by >C=NO-COR ^c11 It is prepared by a method including. R ^c11 is the same as R ^c11 in formula (c4).

The 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 above formula (c5) with an acylating agent.

Examples of the acylating agent 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).

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

[Tue 22]

[Tue 23]

It is preferable that it is 0.5-30 mass % with respect to the mass of the whole solid content of a resin composition, and, as for content of a photoinitiator (C), it is more preferable that it is 1-20 mass %. By setting the content of the photopolymerization initiator (C) within the above range, a resin composition in which defects in pattern shape hardly occur can be obtained.

Moreover, you may combine a photoinitiator (C) with a photoinitiator. As the photoinitiator, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, benzoic acid 2-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-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-5-methoxy Thiol compounds, such as benzothiazole, 3-mercaptopropionic acid, 3-mercapto methyl propionate, pentaerythritol tetramercaptoacetate, and 3-mercaptopropionate, etc. are mentioned. These photoinitiating aids can be used alone or in combination of two or more.

<Pigment (D)>

The resin composition contains a pigment (D). Although it does not specifically limit as a pigment (D), For example, the compound classified as a pigment in the color index (C.I.; published by The Society of Dyers and Colourists), specifically, the following color index (C.I. ) numbered ones are available.

Examples of yellow pigments that can be suitably used include C.I. Pigment Yellow 1 (hereinafter, "C.I. Pigment Yellow" is the same, only numbers are written), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60 , 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119 , 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, and 185 to can be heard

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

Examples of purple pigments that can be suitably used include C.I. Pigment Violet 1 (hereinafter "C.I. Pigment Violet" is the same, only numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50.

Examples of red pigments that can be suitably used include C.I. Pigment Red 1 (hereinafter, "C.I. Pigment Red" is the same, only numbers are written) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49: 2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 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, 2 17, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

Examples of blue pigments that can be suitably used include C.I. Pigment Blue 1 (hereinafter, "C.I. Pigment Blue" is the same, only numbers are written), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, and 66 can be heard

Examples of pigments of the above other colors that 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. Black pigments, such as Pigment Black 7, are mentioned.

Moreover, it is preferable that the resin composition contains a black pigment as a pigment (D). Light-shielding property is provided to the cured film formed by using the resin composition containing a black pigment. For this reason, the resin composition containing a black pigment is suitably used for formation of a black matrix or black column spacer in a liquid crystal display panel, and formation of a bank for partitioning a light emitting layer in an organic EL element.

Examples of black pigments include carbon black, perylene pigments, lactam pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxides, metal sulfides, metal sulfates, or metals. Various pigments are exemplified regardless of organic substances and inorganic substances such as carbonates. Among these black pigments, carbon black is preferable from the viewpoint of easy availability and easy formation of a cured film having excellent light-shielding properties and high electrical resistance.

The hue of the black pigment is not limited to black, which is an achromatic color in terms of color theory, but may be purple-tinged black, bluish-black, or reddish-black.

As carbon black, well-known carbon blacks, such as channel black, furnace black, thermal black, and lamp black, can be used. Moreover, you may use resin-coated carbon black.

As the carbon black, carbon black subjected to a treatment for introducing an acidic group is also preferable. The acidic group introduced into carbon black is a functional group that exhibits acidity according to the definition of Brensted. A carboxy group, a sulfonic acid group, a phosphoric acid group etc. are mentioned as a specific example of an acidic group. The acidic group introduced into carbon black may form a salt. A cation that forms a salt with an acidic group is not particularly limited as long as the object of the present invention is not impaired. 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 ions, potassium ions, and lithium ions, and ammonium ions are preferable.

From the viewpoint of achieving high resistance of a light-shielding cured film formed using a resin composition, among the carbon blacks subjected to the treatment of introducing an acidic group described above, from the group consisting of a carboxylic acid group, a carboxylic acid base, a sulfonic acid group, and a sulfonic acid base. Carbon black having at least one selected functional group is preferred.

The method of introducing an acidic group into carbon black is not particularly limited. As a method of introducing an acidic group, the following method is mentioned, for example.

1) A method of introducing a sulfonic acid group into 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 salt, hydrogen sulfite salt, or the like.

2) A method of diazo-coupling an organic compound having an amino group and an acidic group with carbon black.

3) A method of reacting an organic compound having a halogen atom and an acidic group with carbon black having a hydroxyl group by Williamson's 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 in which carbon black is subjected to a Friedel Crafts reaction using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group, followed by deprotection.

Among these methods, method 2) is preferred because the treatment for introducing an acidic group is easy and safe. As the organic compound having an amino group and an acidic group used in 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 or aminobenzoic acids such as 4-aminobenzoic acid.

The number of moles of acidic groups introduced into carbon black is not particularly limited as long as the object of the present invention is not impaired. The number of moles of acidic groups introduced into carbon black is preferably 1 to 200 mmol, more preferably 5 to 100 mmol per 100 g of carbon black.

Carbon black into which an acidic group has been introduced may be subjected to a coating treatment with a resin. In the case of using a resin composition containing carbon black coated with a resin, it is easy to form a light-shielding cured film having excellent light-shielding properties and insulating properties and having a low surface reflectance. Further, the coating treatment with the resin does not particularly adversely affect the dielectric constant of the light-shielding cured film formed using the resin composition. Examples of resins usable for coating carbon black include thermosetting resins such as phenol resins, melamine resins, xylene resins, diallylphthalate resins, glyptal resins, epoxy resins, and alkylbenzene resins; polystyrene, polycarbonate, polyethylene terephthalate, Polybutylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, polyetherether Thermoplastic resins, such as a ketone, are mentioned. The coating amount of the resin relative to the carbon black is preferably 1 to 30 mass% with respect to the total mass of the carbon black and the mass of the resin.

Moreover, as a black pigment, a perylene-type pigment can also be used suitably. Specific examples of the perylene pigment include a perylene pigment represented by the following formula (d-1), a perylene pigment represented by the following formula (d-2), and a perylene pigment represented by the following formula (d-3). can As a commercial item, product names K0084 and K0086 by BASF, Pigment Black 21, 30, 31, 32, 33 and 34, etc. can be used suitably as a perylene pigment.

[Tue 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. .

[Tue 25]

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

[Tue 26]

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

The compound represented by the above formula (d-1), the compound represented by the formula (d-2), and the compound represented by the formula (d-3) are, for example, Japanese Unexamined Patent Publication No. 62-1753, Japan It can be synthesized using the method described in Japanese Patent Publication No. 63-26784. That is, a heating reaction is performed in water or an organic solvent using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines as raw materials. Then, the target product can be obtained by reprecipitating the obtained preparation in sulfuric acid or recrystallizing it in water, an organic solvent, or a mixed solvent thereof.

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

Moreover, a lactam-type pigment can also be included as a light-shielding agent. As a lactam-type pigment, the compound represented by the following formula (d-4) is mentioned, for example.

[Tue 27]

In formula (d-4), X ^d represents a double bond, is a geometric isomer and is each independently E or Z, and R ^d9 is each independently a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, or a chlorine atom, fluorine atom, carboxy group, or sulfo group, R ^d10 each 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 compound represented by formula (d-4) can be used individually or in combination of 2 or more types.

^Rd9 is preferably bonded to the 6th position of the dihydroindolone ring, and ^Rd11 is preferably bonded to the 4th position of the dihydroindolone ring from the viewpoint of easy preparation of the compound represented by formula (d-4). do. From the same viewpoint, R ^d9 , R ^d10 , and R ^d11 are preferably hydrogen atoms.

The compound represented by formula (d-4) has EE, ZZ, and EZ as geometric isomers, and may be a single compound of these several or a mixture of these geometric isomers.

The compound represented by formula (d-4) can be manufactured by the method described in International Publication No. 2000/24736 and International Publication No. 2010/081624, for example.

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

In addition, fine particles containing a silver tin (AgSn) alloy as a main component (hereinafter referred to as "AgSn alloy fine particles") are also preferably used as the black pigment. The AgSn alloy microparticles need only have an AgSn alloy as a main component, and may contain, for example, Ni, Pd, Au, etc. as other metal components.

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 both chemical stability and blackness are obtained is 3≤x≤4.

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

For x=1, Ag/AgSn=0.4762

When x=3, 3·Ag/Ag3Sn=0.7317

When x=4, 4·Ag/Ag4Sn=0.7843

When x=10, 10 Ag/Ag10Sn=0.9008

becomes

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

This AgSn alloy fine particle can be manufactured using a normal fine particle synthesis method. Examples of fine particle synthesis methods include gas phase reaction method, spray pyrolysis method, atomization method, liquid phase reaction method, lyophilization method, hydrothermal synthesis method and the like.

Although the AgSn alloy fine particles have high insulating properties, depending on the use of the resin composition, the surface may be covered with an insulating film to further enhance the insulating properties. As a material for such an insulating film, metal oxides or organic high molecular compounds are suitable.

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

Moreover, as an organic high molecular compound, resin which has insulating property, for example, polyimide, polyether, polyacrylate, a polyamine compound, etc. are used suitably.

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 properties of the surface of the AgSn alloy fine particles.

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

As the black pigment, the aforementioned perylene-based pigment, lactam-based pigment, and AgSn alloy fine particles may be used alone or in combination thereof.

In addition, the black pigment may contain pigments of colors such as red, blue, green and yellow for the purpose of color tone adjustment and the like. Pigments of other colors of the black pigment can be appropriately selected from known pigments. For example, the above various pigments can be used as pigments of different colors from black pigments. 15 mass % or less is preferable with respect to the total mass of a black pigment, and, as for the usage-amount of the pigment|dye of another color of a black pigment, 10 mass % or less is more preferable.

In order to uniformly disperse the pigment (D) described above in the resin composition, you may further use a dispersing agent. As such a dispersing agent, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersing agent. In particular, when carbon black is used as the pigment (D), it is preferable to use an acrylic resin-based dispersant as the dispersant.

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

In addition, the inorganic pigment and the organic pigment may be used individually or in combination of two or more, but when used in combination, the organic pigment is preferably used in the range of 10 to 80 parts by mass based on 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. It is more preferable to use it in the range of 20-40 mass parts.

Moreover, in a resin composition, you may use combining the pigment (D) and dye. What is necessary is just to select this dye suitably from known materials.

As dyes applicable to the resin composition, for example, azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, etc. can be heard

In addition, these dyes can be dispersed in an organic solvent or the like by laking (salting), and this can be used as the (D) coloring agent.

In addition to these dyes, dyes and the like described in, for example, Japanese Patent Laid-Open No. 2013-225132, Japanese Patent Laid-Open No. 2014-178477, Japanese Unexamined Patent Publication No. 2013-137543, Japanese Unexamined Patent Publication No. 2011-38085, Japanese Unexamined Patent Publication No. 2014-197206, etc. can be used preferably.

The amount of pigment (D) used in the resin composition can be appropriately selected within a range that does not impair the object of the present invention, and is typically preferably 2 to 75% by mass, preferably 3 to 75% by mass, based on the total mass of the solid content of the resin composition. 70 mass % is more preferable.

The pigment (D) is preferably added to the resin composition after forming a dispersion in which the pigment (D) is dispersed at an appropriate concentration in the presence or absence of a dispersant.

In addition, in this specification, the usage amount of the above-mentioned pigment (D) can be defined as a value including the dispersant present therein.

<Silane coupling agent (E)>

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

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

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

(In 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, and R ^e4 is a divalent organic group, and R ^e5 is a Brensted acid group, an alcoholic hydroxyl group, an amino group, or a carbamoyl group.)

It includes an alkoxysilane compound represented by

By blending the silane coupling agent containing the compound represented by the formula (e1) with the resin composition, when patterning by the photolithography method is performed using the resin composition, the formed patterned cured film adheres well to the substrate. can be made, and generation of development residues in unexposed areas can be suppressed.

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

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

Among 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 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, preferably linear.

Preferred specific examples of R ^e3 include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. -diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, and decane-1,10-diyl group.

Among these, the compound represented by formula (e1) is easy to obtain and synthesize, and the effect of sufficient pattern adhesion and the effect of suppressing the generation of development residue are easy to obtain, so ethane-1,2-diyl group, propane-1 ,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane 1,6-diyl group are preferred, and ethane-1,2-diyl group and propane-1,3 A -diyl group and a butane-1,4-diyl group are more preferred, and a propane-1,3-diyl group is particularly preferred.

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

Since these groups easily form hydrogen bonds, groups represented by -CO-R ^e4 -R ^e5 at the terminals of a plurality of compounds represented by formula (e1) bonded to the substrate surface are blocked through hydrogen bonds. easy.

It is thought that the block formed by the groups represented by -CO-R ^e4 -R ^e5 prevents the development residue from strongly binding to the substrate surface in the unexposed area, and suppresses the generation of the development residue.

Moreover, the group represented by -CO-R ^e4 -R ^e5 tends to form a hydrogen bond even with a cured film. For this reason, it is thought that the cured film formed using the resin composition containing the compound represented by Formula (e1) adheres favorably to the substrate surface.

Preferred specific examples of the Brensted acidic group as ^Re5 include a carboxy 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 Brensted acidic group is preferred, and a carboxy group is more preferred, because desired effects are easily obtained.

The divalent organic group as ^Re4 is not particularly limited as long as the object of the present invention is not impaired. The number of carbon atoms in the divalent organic group as ^Re4 is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less, and particularly preferably 1 or more and 12 or less.

Examples of the divalent organic group as ^Re4 include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, and a divalent heterocyclic group.

All of these groups may have a substituent.

When the divalent aliphatic hydrocarbon group, divalent aromatic hydrocarbon group, and divalent heterocyclic group as ^Re4 have a substituent, suitable examples of the substituent include an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, A monoalkylamino group having 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, an alkyl group having 1 to 6 carbon atoms, carbon A dialkylamino group having an alkyl group of 1 to 6 atoms, a halogen, a nitro group, a cyano group, and the like are exemplified.

The divalent aliphatic hydrocarbon group as ^Re4 may be linear, branched, cyclic or cyclic, and may contain a combination of these structures.

Moreover, the divalent aliphatic hydrocarbon group as ^Re4 may contain an unsaturated double bond.

Suitable examples in the case where the divalent aliphatic hydrocarbon group as ^Re4 is a chain group include a methylene group, an ethane-1,2-diyl group, an ethene-1,2-diyl group, a propane-1,3-diyl group, and a propane-1,2-diyl group. -Diyl group, propane-2,2-diyl group, and butane-1,4-diyl group, etc. are mentioned.

When the divalent aliphatic hydrocarbon group as ^Re4 is cyclic, preferable groups include monocycloalkanes, bicycloalkanes, tricycloalkanes, and groups obtained by removing two hydrogen atoms from tetracycloalkanes and the like.

Specifically, from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane, etc., except for two hydrogen atoms, can lift

Preferable examples of the divalent aromatic hydrocarbon group as ^Re4 include a phenylene group, a naphthalenediyl group, a phenanthrendiyl group, anthracenediyl group, and a pyrendiyl group.

When ^Re4 is a divalent heterocyclic group, the heterocyclic group is preferably a 5-membered or 6-membered monocycle containing at least one of N, S, and O, or a group formed by condensation of such monocycles or a benzene ring.

Examples of such a divalent heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, Benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzooxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinoline , and quinoxaline, etc., wherein two hydrogen atoms are removed.

As ^Re44 , it is preferably a divalent aromatic hydrocarbon group from the viewpoint of good effect of pattern adhesion and suppression of development residue.

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

A Brensted acidic group, an alcoholic hydroxyl group, an amino group, or a carbamoyl group as ^Re5 is a functional group capable of forming a hydrogen bond with a carbonyl group.

Therefore, in a divalent aromatic hydrocarbon group, if the relationship between the position of a carbon atom to which one bond hand is bonded and the position of a carbon atom to which the other bond bond is bonded is an adjacent position or a peri-position, a plurality of expressions When the compound represented by (e1) is bonded to a position adjacent to the substrate, R ^e5 in the compound represented by formula (e1) easily forms a hydrogen bond with the carbonyl group in the compound represented by other formula (e1).

On the other hand, when a plurality of compounds represented by Formula (e1) are bonded to adjacent positions on a substrate, π-π stacking or the like may occur between a plurality of ^{Ree4s because Ree4 is} a divalent aromatic group. .

For the reasons described above, if the positional relationship of the two bonds in the divalent aromatic hydrocarbon group is adjacent or perimetric, -CO-R ^e4 -R ^e5 at the terminal of the compound represented by formula (e1) It is presumed that the group represented by is likely to exhibit a self-organizing behavior, and a block composed of a plurality of groups represented by -CO-R ^e4 -R ^e5 is easily formed on the substrate surface.

In this case, the block composed of groups represented by -CO-R ^e4 -R ^e5 adheres the cured film to the substrate well by hydrogen bonding with the cured film or interaction between aromatic rings in the exposed portion, and mino In the miner, direct interaction between the substrate and the developed residue is inhibited, and it is thought that the generation of the developed residue is suppressed.

Suitable specific examples of the divalent aromatic hydrocarbon group as R ^e4 include o-phenylene group, m-phenylene group, p-phenylene group, naphthalene-1,2-diyl group, naphthalene-1,3-diyl group, naphthalene-1, 4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-1,7-diyl group, naphthalene-1,8-diyl group, naphthalene-2,3-diyl group, A naphthalene-2,6-diyl group and a naphthalene-2,7-diyl group are mentioned.

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 divalent aromatic hydrocarbon group, the relationship between the position of the carbon atom to which one bond hand is bonded and the position of the carbon atom to which the other bond bond is bonded is preferably an adjacent position or a peri-position. because it does

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

[Tue 28]

The compound represented by the formula (e1) described above can be used in combination with various silane coupling agents having structures other than the structure represented by the formula (e1). As a silane coupling agent which can be used together with the compound represented by formula (e1), it can select suitably from silane coupling agents conventionally used for various purposes.

Suitable examples of such silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, and n-butyl. monoalkyltrialkoxysilanes such as trimethoxysilane and n-butyltriethoxysilane; dialkyldialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; monophenyltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane; diphenyldialkoxysilanes such as diphenyldimethoxysilane and diphenyldiethoxysilane; monovinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acryloxy, such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane alkylmonoalkyldialkoxysilanes; (meth)acryloxyalkyltrialkoxysilanes such as 3-acryloxypropyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltri Ethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3 -Aminopropylmethyldiethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 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 ketiminesilane in which these amino groups are protected with aldehyde or the like; Alkyltri(or di)alkoxysilanes containing non-alicyclic epoxyfluorenylidene groups such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane ; non-alicyclic epoxy group-containing alkyl monoalkyldialkoxysilanes such as 3-glycidoxypropylmethyldiethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)methyldimethoxysilane, 2-(3,4-epoxycyclohexyl)methyldiethoxysilane and other alicyclic epoxy group-containing alkyltri(or di)alkoxysilanes; 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane and other alicyclic epoxy group-containing alkyl monoalkyldialkoxysilanes; [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, etc. silane; mercaptoalkyltrialkoxysilanes such as 3-mercaptopropyltrimethoxysilane; mercaptoalkyl monoalkyldialkoxysilanes such as 3-mercaptopropylmethyldimethoxysilane; ureidoalkyltrialkoxysilanes such as 3-ureidopropyltriethoxysilane; isocyanate alkyltrialkoxysilanes such as 3-isocyanate propyltriethoxysilane; isocyanurate-containing trialkoxysilanes such as tris-(trimethoxysilylpropyl)isocyanurate and tris-(triethoxysilylpropyl)isocyanurate; 3-trimethoxysilylpropyl succinic acid anhydride, other acid anhydride groups (e.g., cyclohexanedicarboxylic acid anhydride group, 4-methyl-cyclohexanedicarboxylic acid anhydride group, 5-methyl-cyclohexanedicarboxylic acid anhydride group, Alkyl trialkoxysilanes containing an acid anhydride group such as trialkoxysilane having a cycloheptane dicarboxylic acid anhydride group, 7-oxa-bicycloheptane dicarboxylic acid anhydride group, phthalic anhydride group, etc.); As the carboxy group, a succinic acid group, or a half ester group thereof, 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 An alkyltrialkoxysilane containing a carboxyl group having a half ester group thereof, a bicycloheptane dicarboxylic acid group, or a half ester group thereof, a 7-oxa-bicycloheptane dicarboxylic acid group, or a half ester group thereof, a phthalic acid group, or a half ester group thereof. ; Alkyltrialkoxysilanes containing an imide group such as N-tert-butyl-3-(3-trimethoxysilylpropyl)succinic acid imide; Alkyltrialkoxysilanes containing a carbamate group such as (3-trimethoxysilylpropyl)-t-butyl carbamate and (3-triethoxysilylpropyl)-tert-butyl carbamate; etc. can be mentioned.

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, and particularly preferably 1 to 5% by mass, based on the total mass of the solid content of the resin composition. do.

By using the silane coupling agent (E) in an amount within this range, it is easy to adhere the formed pattern to the substrate particularly well, and it is easy to particularly easily suppress the occurrence of development residues in unexposed areas.

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% by mass or more, more preferably 15% by mass or more, and particularly preferably 30% by mass or more. do.

In addition, the upper limit of the ratio of the mass of the compound represented by the formula (e1) to the total mass of the silane coupling agent (E) is not particularly limited. It can be 85% by mass or less.

Moreover, 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 an amount within the above range and the silane coupling agent (E) in the above ratio, it is easy to adhere the formed pattern to the substrate well, and development residue is generated in the unexposed area easy to suppress

Further, in the resin composition, the content of the compound represented by formula (e1) is preferably 0.01 to 10% by mass, more preferably 0.5 to 6% by mass, and 1 to 5% by mass relative to the total mass of the solid content of the resin composition. Mass % is particularly preferred.

By using the compound represented by formula (e1) in an amount within this range, it is easy to adhere the formed pattern to the substrate particularly well, and it is easy to particularly suppress the occurrence of development residue in unexposed areas.

<organic solvent (S)>

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

Specifically as the organic solvent (S), 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-propyl 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 (poly)alkylene glycol monoalkyl ethers such as tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; 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), propylene glycol monoethyl ether acetate (poly ) 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; lactate alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-Hydroxy-2-methylethylpropionate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, ethoxyacetate ethyl, hydroxyacetate ethyl, 2 -Hydroxy-3-methylbutanoate, 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, benzyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl 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-methyl-2-pyrrolidone, N,N-dimethylformamide, 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; etc. can be mentioned.

Among these, alkylene glycol monoalkyl ethers, 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, Other ethers and other esters described above, such as benzyl acetate, are more preferred.

Moreover, it is also preferable that the organic solvent (S) contains a nitrogen-containing polar organic solvent from points, such as the solubility of each component and the dispersibility of the pigment (D). As the nitrogen-containing polar organic solvent, N,N,N',N'-tetramethylurea or the like can be used.

These solvents can 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 at a concentration that can be applied to a substrate or the like depending on the coating film thickness. The viscosity of the resin composition is preferably 5 to 500 cp, more preferably 10 to 50 cp, and still more preferably 20 to 30 cp. Moreover, it is preferable that it is 5-100 mass %, and, as for solid content concentration, it is more preferable that it is 15-50 mass %.

＜Other ingredients＞

Additives, such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, an antifoaming agent, and an epoxy compound, can be contained in the resin composition as needed. As any additive, conventionally known ones can be used.

Examples of the surfactant include compounds such as anionic, cationic, and nonionic compounds, examples of thermal polymerization inhibitors include hydroquinone and hydroquinone monoethyl ether, and examples of antifoaming agents include silicone 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 mixing them uniformly with a stirrer. Furthermore, you may filter using a filter so that the obtained mixture may become more uniform.

≪Method for producing a 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 manufacturing method of a cured film,

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

A step of positionally selectively exposing the coated film;

A step of developing the exposed coating film to form a patterned cured film;

A method including a step of baking the patterned cured film is exemplified.

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

The applied resin composition is dried as necessary to form a coating film. The drying method is not particularly limited, and examples include (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) a method of drying at room temperature for several hours to several days. A method of leaving it to stand, (3) a method of removing the solvent by placing it in a warm air heater or an infrared heater for several tens of minutes to several hours, and the like.

Then, the coating film is exposed to light. Exposure is performed by irradiating active energy rays such as ultraviolet rays and excimer laser light. Exposure is position-selectively performed, for example, by a method of exposing through a negative mask. 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.

Further, when exposing the entire surface of the coating film, a cured film having a shape corresponding to the shape of the coating film is formed without being patterned.

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

Next, baking (post-baking) is performed for the patterned cured film. The baking temperature is not particularly limited, but is preferably 180 to 250°C and more preferably 220 to 230°C. 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 containing the pigment (D) formed in this way can be suitably used as a black matrix in a color filter or a colored film such as RGB, depending on the color of the pigment (D).

[ Example ]

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

[Preparation Example 1]

First, in a 500 ml four-necked flask, bisphenol fluorene type epoxy resin (epoxy equivalent 235) 235 g, tetramethylammonium chloride 110 mg, 2,6-di-tert-butyl-4-methylphenol 100 mg, and acrylic acid 72.0 g was added, and heated and dissolved at 90 to 100° C. while blowing air into it at a rate of 25 ml/min. Next, while the solution was in a cloudy state, the temperature was gradually raised and heated to 120°C to completely dissolve the solution. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. In the meantime, the acid value was measured and heating and stirring were continued until it became less than 1.0 mgKOH/g. It took 12 hours for the acid value to reach the target value. And it cooled to room temperature, and the bisphenol fluorene type|mold epoxy acrylate represented by the following formula which was colorless and transparent and was solid was obtained.

[Tue 29]

Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene-type epoxy acrylate obtained in this way and dissolved, and then 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed. And, the temperature was gradually raised and reacted at 110 ~ 115 ℃ for 4 hours. After confirming disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, and it was made to react at 90 degreeC for 6 hours, and resin A-1 was obtained. Disappearance of the acid anhydride group was confirmed by the IR spectrum.

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

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

Resin A-1 obtained in the said preparation example 1 was used as cardo resin.

As the novolak resin, TO-547 (trade name) manufactured by Sumitomo Bakelite Co., Ltd. was used. TO-547 is a cresol novolak resin of Mw30000 obtained by condensation reaction by adding oxalic acid and 37% by mass formalin to a mixture of 90 mol% m-cresol and 10 mol% 2,3,5-trimethylphenol.

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

In Examples and Comparative Examples, as the photopolymerization initiator (C), OXE-02 (trade name, manufactured by BASF, O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazole-3 -yl] ethane oxime) was used.

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

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

In addition, in Table 1 of this Example section, the numerical value is described about the total value of the solid content of this pigment and a dispersant.

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

E1: a compound of the formula

[Tue 30]

E2: 3-glycidoxypropyltrimethoxysilane

E3: 3-phenylaminopropyltrimethoxysilane

The alkali-soluble resin (A), the photopolymerizable compound (B), the photopolymerization initiator (C), the pigment (D), and the type and amount of the (E) epoxy compound shown in Table 1, respectively, in the amount shown in Table 1, respectively. was dissolved and dispersed in (S) an organic solvent so that the solid content concentration was 15% by mass, and resin compositions of Examples and Comparative Examples were obtained.

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

Using the obtained resin composition, adhesion of the patterned cured film to the substrate and generation of residue in unexposed areas were evaluated according to the following method. These evaluation results are written in Table 1.

<Adhesion of the patterned cured film to the substrate>

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

Then, using a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the exposure gap was set to 250 μm, and the coating film was irradiated with ultraviolet rays through a mask for line pattern formation having a line portion having the following width did. The exposure amount was 40 mJ/cm ² .

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

◎: A line pattern with a width of 2 µm or less is in close contact.

○: A line pattern with a width of 3 to 5 μm is in close contact with each other.

(triangle|delta): The line pattern of 6-10 micrometer width is closely_contact|adhering.

x: A line pattern with a width of 11 μm or more is in close contact.

<Generation of residues in unexposed areas>

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

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

After immersing the coated film after exposure for 60 seconds in a 0.04% by mass KOH aqueous solution at 25°C, a matrix having a dimension of 11 µm was formed, and the number of residues that could be confirmed in the matrix was counted. Based on the number of residues measured, the generation of residues after development was evaluated according to the following criteria.

◎: 0 to 10 residues present.

○: 11 to 20 residues present.

△: There are 21 to 40 residues.

×: 41 or more residues are present.

According to the embodiment, (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 are included. It was found that the resin composition to be used can form a pattern with good adhesion to the substrate and suppress the generation of development residues in unexposed areas.

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 the silane coupling agent (E) does not contain a compound having a predetermined structure, adhesion to the substrate It turns out that it is difficult to achieve both the formation of this favorable pattern and suppression of the generation of development residues in unexposed areas.

Claims (8)

An alkali-soluble resin (A);
A photopolymerizable compound (B);
A photopolymerization initiator (C);
A pigment (D);
Silane Coupling Agent (E)
As a resin composition comprising a,
The silane coupling agent (E) has the following formula (e1):
(R ^e1 O) _a (R ^e2 ) _3-a Si-R ^e3 -NH-CO-R ^e4 -R ^e5 ... (e1)
(In 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, and R ^e4 is a divalent aromatic hydrocarbon group, and the relationship between the position of the carbon atom to which one bond hand bonds in the divalent aromatic hydrocarbon group and the position of the carbon atom to which the other bond bond bond is adjacent or peri-position, , R ^e5 is a Brensted acidic group, an alcoholic hydroxyl group, an amino group, or a carbamoyl group.)
A resin composition comprising an alkoxysilane compound represented by The method of claim 1,
The resin composition in which the divalent 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 of claim 1,
The resin composition in which R ^e5 is a carboxyl group. A cured film obtained by curing the resin composition according to any one of claims 1 to 3. A color filter comprising the cured film of claim 4. A step of forming a coating film by applying the resin composition according to any one of claims 1 to 3;
A step of positionally selectively exposing the coating film;
A step of developing the exposed coating film to form a patterned cured film;
A method for producing a cured film comprising a step of baking the patterned cured film. delete delete