CN107272335B - Photosensitive resin composition - Google Patents

Abstract

The present invention relates to a photosensitive resin composition. The invention provides a photosensitive resin composition which can inhibit the precipitation of resin with a Cardo structure and can form a smooth cured film; a cured film formed from a cured product of the photosensitive resin composition; and a method for forming a cured film using the photosensitive resin composition. The photosensitive resin composition comprises (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (S) a solvent, wherein the alkali-soluble resin (A) contains a resin having a Cardo structure, and the photosensitive resin composition comprises (L) a low-boiling solvent having a boiling point of less than 180 ℃ under atmospheric pressure and (H) a high-boiling solvent having a boiling point of 180 ℃ to 300 ℃ under atmospheric pressure, which are used as the (S) solvent, in respective predetermined amounts, and the (H) high-boiling solvent contains a compound having an aromatic hydrocarbon ring and an ester bond.

Description

Photosensitive resin composition

Technical Field

The present invention relates to a photosensitive resin composition, a cured film formed from a cured product of the photosensitive resin composition, and a method for forming a cured film using the photosensitive resin composition.

Background

In display devices such as liquid crystal display devices and organic EL display devices, various curable compositions using transparent or colored insulating materials have been used. Examples of the colored insulating material include: black column spacers (cell gaps) for keeping the interval between 2 substrates constant, black matrices for dividing colored regions in a color filter (color filter), and the like.

As a method for forming an insulating material used for the above-described panel for a display device, for example, a method using a negative photosensitive resin composition is proposed.

Specifically, it has been proposed to use a negative photosensitive resin composition containing a photopolymerizable compound, a photopolymerization initiator, an acrylic resin fine particle dispersion in which acrylic resin fine particles are dispersed, and a solvent (see patent document 1). Patent document 1 proposes the use of a resin having a Cardo structure as a photopolymerizable compound, in order to facilitate the formation of a cured film having excellent balance among heat resistance, mechanical properties, solvent resistance, chemical resistance, and the like.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2011-

Disclosure of Invention

Problems to be solved by the invention

Here, in many cases, a high degree of smoothness is required for an insulating material (particularly, an insulating material containing a pigment). However, when a cured film is formed using the negative photosensitive resin composition described in patent document 1, it may be difficult to form a smooth cured film depending on the type of solvent. In addition, when the photosensitive resin composition contains a resin having a Cardo structure, there is a problem that precipitation of the resin having a Cardo structure is likely to occur.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a photosensitive resin composition capable of suppressing precipitation of a resin having a Cardo structure and forming a smooth cured film; a cured film formed from a cured product of the photosensitive resin composition; and a method for forming a cured film using the photosensitive resin composition.

Means for solving the problems

The present inventors have found that the above problems can be solved by using, as the (S) solvent, a (L) low-boiling solvent having a boiling point of less than 180 ℃ under atmospheric pressure and a (H) high-boiling solvent having a boiling point of 180 ℃ to 300 ℃ under atmospheric pressure in a photosensitive resin composition containing (a) an alkali-soluble resin containing a resin having a Cardo structure, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (S) a solvent in predetermined amounts, and by including a compound having an aromatic hydrocarbon ring and an ester bond in the (H) high-boiling solvent, thereby completing the present invention.

The invention of claim 1 is a photosensitive resin composition, which comprises (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator and (S) a solvent,

(A) the alkali-soluble resin contains a resin having a Cardo structure,

the (S) solvent comprises (L) a low-boiling solvent having a boiling point of less than 180 ℃ under atmospheric pressure and (H) a high-boiling solvent having a boiling point of 180 ℃ or higher and 300 ℃ or lower under atmospheric pressure,

(H) the high boiling point solvent contains a compound having an aromatic hydrocarbon ring and an ester bond,

(H) the content of the high-boiling solvent in the (S) solvent is 1 to 30 mass%.

The invention of the 2 nd embodiment relates to a cured film, which is formed by the photosensitive resin composition of the 1 st embodiment of the cured product.

The 3 rd embodiment of the present invention is a cured film formed from a cured product of the photosensitive resin composition according to the 1 st embodiment containing (D) a pigment.

The 4 th aspect of the present invention is a method for forming a cured film, including the steps of:

a step of forming a coating film by coating the photosensitive resin composition according to claim 1 on a substrate; and

and exposing the coating film.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided a photosensitive resin composition capable of suppressing precipitation of a resin having a Cardo structure and forming a smooth cured film; a cured film formed from a cured product of the photosensitive resin composition; and a method for forming a cured film using the photosensitive resin composition.

Detailed Description

Photosensitive resin composition

The photosensitive resin composition comprises (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (S) a solvent.

The (S) solvent includes (L) a low-boiling solvent having a boiling point of less than 180 ℃ under atmospheric pressure, and (H) a high-boiling solvent having a boiling point of 180 ℃ or higher and 300 ℃ or lower under atmospheric pressure.

(H) The high boiling point solvent contains a compound having an aromatic hydrocarbon ring and an ester bond.

The essential or optional components contained in the photosensitive resin composition will be described below.

< A) alkali-soluble resin >

The alkali-soluble resin means: a resin film having a film thickness of 1 μm was formed on a substrate using a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20 mass%, and the film thickness was dissolved with a resin having a film thickness of 0.01 μm or more when the substrate was immersed in a KOH aqueous solution having a concentration of 0.05 mass% for 1 minute.

(A) The alkali-soluble resin must contain (a1) a resin having a Cardo structure. By using a photosensitive resin composition containing (a1) a resin having a Cardo structure as (a) an alkali-soluble resin, a cured film having excellent balance among heat resistance, mechanical properties, solvent resistance, chemical resistance and the like can be easily formed.

The resin having a Cardo structure (a1) is not particularly limited, and conventionally known resins can be used. Among them, a resin represented by the following formula (a-1) is preferable.

In the above formula (a-1), X^aRepresents a group represented by the following formula (a-2).

In the above formula (a-2), R^a1Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms or a halogen atom, R^a2Each independently represents a hydrogen atom or a methyl group, W^aRepresents a single bond or a group represented by the following formula (a-3).

In the above formula (a-1), Y^aThe residue is obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic anhydride. Examples of the dicarboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, chlorendic anhydride (chlorendic anhydride), methyl tetrahydrophthalic anhydride, glutaric anhydride, and the like.

In the above formula (a-1), Z^aThe residue is obtained by removing 2 acid anhydride groups from a tetracarboxylic dianhydride. Examples of the tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, biphenyl ether tetracarboxylic acid dianhydride, and the like.

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

(A1) The weight average molecular weight (Mw: measured in terms of polystyrene by Gel Permeation Chromatography (GPC)., the same as in the present specification) of the resin having a Cardo structure is preferably 1000 to 40000, and more preferably 2000 to 30000. By setting the above range, not only good developability but also sufficient heat resistance and film strength can be obtained.

The mass ratio of the resin having a Cardo structure (a1) to the total mass of the alkali-soluble resin (a) is preferably 50 mass% or more, more preferably 70 mass% or more, particularly preferably 90 mass% or more, and may be 100 mass%.

(A) When the alkali-soluble resin contains a resin other than the resin having a Cardo structure (a1), the resin other than the Cardo structure is not particularly limited as long as it is a resin having a predetermined alkali-solubility.

From the viewpoint of easy formation of a film having excellent mechanical strength and adhesion to a substrate, (a2) a copolymer obtained by polymerizing at least (a1) an unsaturated carboxylic acid, together with (a1) a resin having a Cardo structure, can be suitably used as (a) the alkali-soluble resin.

Examples of the unsaturated carboxylic acid (a1) include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; anhydrides of these dicarboxylic acids; and so on. Among these unsaturated carboxylic acids, (meth) acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, easiness of obtaining, and the like. These (a1) unsaturated carboxylic acids may be used alone or in combination of 2 or more.

(A2) The copolymer may be a copolymer of (a1) an unsaturated carboxylic acid and (a2) an alicyclic epoxy group-containing unsaturated compound. The alicyclic epoxy group-containing unsaturated compound (a2) is not particularly limited as long as it is an alicyclic epoxy group-containing unsaturated compound. The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include cyclopentyl and cyclohexyl. Examples of the polycyclic alicyclic group include norbornyl (norbonyl), isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl. These alicyclic epoxy group-containing unsaturated compounds (a2) may be used alone or in combination of 2 or more.

Specifically, examples of the alicyclic epoxy group-containing unsaturated compound (a2) include compounds represented by the following formulae (a2-1) to (a 2-15). Among them, in order to moderate the developability, compounds represented by the following formulae (a2-1) to (a2-5) are preferable, and compounds represented by the following formulae (a2-1) to (a2-3) are more preferable.

In the above formula, R^a20Represents a hydrogen atom or a methyl group, R^a21Represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R^a22Represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and t represents an integer of 0 to 10. As R^a21Preferred is a linear or branched alkylene group, such as methylene, ethylene, propylene, 1, 4-butylene, ethylethylene, 1, 5-pentylene, and 1, 6-hexylene. As R^a22Preferred are, for example, methylene, ethylene, propylene, 1, 4-butylene, ethylethylene, 1, 5-pentylene, 1, 6-hexylene, phenylene, cyclohexylene, -CH₂-Ph-CH₂- (Ph represents phenylene).

(A2) The copolymer may be obtained by copolymerizing the unsaturated carboxylic acid (a1) and the alicyclic epoxy group-containing unsaturated compound (a2) with the alicyclic group-containing unsaturated compound (a3) having no epoxy group.

The alicyclic group-containing unsaturated compound (a3) is not particularly limited as long as it is an alicyclic group-containing unsaturated compound. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include cyclopentyl and cyclohexyl. Examples of the polycyclic alicyclic group include adamantyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl. These alicyclic group-containing unsaturated compounds (a3) may be used alone or in combination of 2 or more.

Specifically, examples of the alicyclic group-containing unsaturated compound (a3) include compounds represented by the following formulae (a3-1) to (a 3-7). Among them, in order to moderate the developability, preferred are compounds represented by the following formulae (a3-3) to (a3-8), and more preferred are compounds represented by the following formulae (a3-3) and (a 3-4).

In the above formula, R^a23Represents a hydrogen atom or a methyl group, R^a24Represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R^a25Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As R^a24The alkylene group is preferably a single bond, a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a1, 4-butylene group, an ethylethylene group, a1, 5-pentylene group, or a1, 6-hexylene group. As R^a25Preferably, for example, methyl and ethyl.

The copolymer (a2) may be obtained by polymerizing the unsaturated carboxylic acid (a1), the unsaturated compound (a2) containing an alicyclic epoxy group, the unsaturated compound (a3) containing an alicyclic group, and the unsaturated compound (a4) containing an epoxy group, which does not have an alicyclic group.

Examples of the unsaturated compound having an epoxy group (a4) include epoxy alkyl esters of (meth) acrylic acid such as glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, and 6, 7-epoxyheptyl (meth) acrylate; epoxy alkyl esters of α -alkylacrylates such as α -ethylacrylate, α -n-propylacrylate, α -n-butylacrylate, and 6, 7-epoxyheptyl α -ethylacrylate; and so on. Among them, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate and 6, 7-epoxyheptyl (meth) acrylate are preferable from the viewpoints of copolymerization reactivity, strength of the cured resin and the like. These epoxy group-containing unsaturated compounds (a4) may be used alone or in combination of 2 or more.

The copolymer (a2) may be obtained by further polymerizing a compound other than the above-mentioned compounds. Examples of such other compounds include (meth) acrylates, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds may be used alone or in combination of 2 or more.

Examples of the (meth) acrylic esters include linear or branched alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, pentyl (meth) acrylate, and tert-octyl (meth) acrylate; chloroethyl (meth) acrylate, 2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate; and so on.

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

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; and so on.

Examples of the vinyl ethers include alkyl vinyl ethers such as 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, and the like; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2, 4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthracenyl ether; and so on.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl diethylacetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl β -phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

Examples of the styrene include styrene; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene and acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; halogenated styrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; and so on.

The proportion of the structural unit derived from the unsaturated carboxylic acid (a1) in the copolymer (A2) is preferably 1 to 50% by mass, more preferably 5 to 45% by mass.

In the case where the copolymer (a2) includes the structural unit derived from the alicyclic epoxy group-containing unsaturated compound (a2) and the structural unit derived from the epoxy group-containing unsaturated compound (a4), the sum of the proportion of the structural unit derived from the alicyclic epoxy group-containing unsaturated compound (a2) in the copolymer (a2) and the proportion of the structural unit derived from the epoxy group-containing unsaturated compound (a4) in the copolymer (a2) is preferably 71 mass% or more, more preferably 71 to 95 mass%, and still more preferably 75 to 90 mass%. In particular, the proportion of the structural unit derived from the alicyclic epoxy group-containing unsaturated compound (a2) in the copolymer (a2) is preferably 71 mass% or more, and more preferably 71 to 80 mass% by weight. By setting the proportion of the structural unit derived from the alicyclic epoxy group-containing unsaturated compound (a2) in the above range, the stability of the photosensitive resin composition over time can be further improved.

When the copolymer (a2) contains a structural unit derived from the alicyclic group-containing unsaturated compound (A3), the proportion of the structural unit derived from the alicyclic group-containing unsaturated compound (A3) in the copolymer (a2) is preferably 1 to 30% by mass, more preferably 5 to 20% by mass.

(A2) The weight average molecular weight of the copolymer is preferably 2000 to 200000, and more preferably 3000 to 30000. When the amount is within the above range, the photosensitive resin composition tends to have a good balance between film forming ability and developability after exposure.

As the resin other than the resin (a1) having a Cardo structure, which is used as the alkali-soluble resin (a), a resin including a copolymer (A3) or a copolymer (a4) in which the copolymer (A3) is a copolymer containing at least a structural unit derived from the above-mentioned unsaturated carboxylic acid (a1) and a structural unit having a site polymerizable with the later-described photopolymerizable monomer (B), and the copolymer (a4) is a copolymer containing at least a structural unit derived from the above-mentioned unsaturated carboxylic acid (a1), a structural unit derived from the above-mentioned unsaturated compound having an alicyclic epoxy group (a2) and/or an unsaturated compound having an epoxy group (a4), and a structural unit having a site polymerizable with the later-described photopolymerizable monomer (B) can be suitably used. When the alkali-soluble resin (a) includes the copolymer (A3) or the copolymer (a4), the adhesion between a film formed using the photosensitive resin composition and a substrate and the mechanical strength of a cured film obtained using the photosensitive resin composition can be improved.

(A3) The copolymer (a4) and the copolymer (a4) may be obtained by further copolymerizing (meth) acrylates, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like, which are described for the copolymer (a2) as other compounds.

The structural unit having a site polymerizable with (B) a photopolymerizable monomer is preferably a structural unit having an ethylenically unsaturated group as a site polymerizable with (B) a photopolymerizable monomer. The copolymer (a3) can be prepared by reacting at least a part of the carboxyl groups contained in the polymer containing the structural unit derived from the unsaturated carboxylic acid (a1) with the unsaturated compound (a2) containing an alicyclic epoxy group and/or the unsaturated compound (a4) containing an epoxy group. The copolymer (a4) can be prepared by reacting (a1) the unsaturated carboxylic acid with at least a part of the epoxy groups in a copolymer having the structural unit derived from the unsaturated carboxylic acid (a1) and the structural unit derived from the unsaturated compound (a2) containing an alicyclic epoxy group and/or the unsaturated compound (a4) containing an epoxy group.

The proportion of the structural unit derived from the unsaturated carboxylic acid (a1) in the copolymer (A3) is preferably 1 to 50% by mass, more preferably 5 to 45% by mass. The proportion of the structural unit having a site polymerizable with the photopolymerizable monomer (B) in the copolymer (a3) is preferably 1 to 45% by mass, more preferably 5 to 40% by mass. When the copolymer (a3) contains the respective structural units in the above ratio, a photosensitive resin composition capable of forming a film having excellent adhesion to a substrate can be easily obtained.

The proportion of the structural unit derived from the unsaturated carboxylic acid (a1) in the copolymer (A4) is preferably 1 to 50% by mass, more preferably 5 to 45% by mass. The proportion of the structural unit derived from the alicyclic epoxy group-containing unsaturated compound (a2) and/or the epoxy group-containing unsaturated compound (a4) in the copolymer (a4) is preferably 55% by mass or more, more preferably 71% by mass or more, and particularly preferably 71 to 80% by mass.

The proportion of the structural unit having a site polymerizable with the photopolymerizable monomer (B) in the copolymer (a4) is preferably 1 to 45% by mass, more preferably 5 to 40% by mass. When the copolymer (a4) contains the respective structural units in the above ratio, a photosensitive resin composition capable of forming a film having excellent adhesion to a substrate can be easily obtained.

(A3) The weight average molecular weight of the copolymer (A4) and the copolymer (B) is preferably 2000 to 50000, more preferably 5000 to 30000. When the amount is within the above range, the photosensitive resin composition tends to have a good balance between film forming ability and developability after exposure.

The content of the alkali-soluble resin (A) is preferably 40 to 85 mass%, more preferably 45 to 75 mass%, based on the solid content of the photosensitive resin composition. When the total amount of the content of the alkali-soluble resin (a), the content of the photopolymerizable monomer (B), and the content of the photopolymerization initiator (C) is 100 parts by mass, the alkali-soluble resin (a) is preferably blended in the photosensitive resin composition so that the content of the photopolymerizable monomer (B) in the photosensitive resin composition is 5 to 50 parts by mass.

[ photopolymerizable Compound (B) ]

The photopolymerizable compound includes a monofunctional compound and a polyfunctional compound.

Examples of the monofunctional compound include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, t-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3, 3-tetrafluoropropyl (meth) acrylate, half-esters of (meth) acrylic acid of phthalic acid derivatives, and the like. These monofunctional compounds may be used alone or in combination of 2 or more.

On the other hand, examples of the polyfunctional compound include 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, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol 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, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 6-acrylate, pentaerythritol tri (meth) acrylate, glycerol di (meth) acrylate, glycerol (meth) acrylate, pentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol hexaacrylate, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, and the like, Dipentaerythritol hexa (meth) acrylate, 2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., toluene diisocyanate), the reaction product of trimethyl 1, 6-hexamethylene diisocyanate and 1, 6-hexamethylene diisocyanate with 2-hydroxyethyl (meth) acrylate, and mixtures thereof, Polyfunctional compounds such as methylenebis (meth) acrylamide, (meth) acrylamidomethylene ether, and condensates of polyhydric alcohols and N-methylol (meth) acrylamide, and 1,3, 5-triacryloylhexahydro-s-triazine (triacrylformal). These polyfunctional compounds may be used alone or in combination of 2 or more.

The content of the photopolymerizable compound (B) is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, based on the solid content of the photosensitive resin composition. By setting the above range, the balance of sensitivity, developability, and resolution tends to be easily obtained.

[ C ] photopolymerization initiator

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

Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl propane-1-one, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl propane-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methyl propane-1-one, 2-dimethoxy-1, 2-diphenylethane-1-one, bis (4-dimethylaminophenyl) one, and, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl (morpholino) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butan-1-one, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyloxime), (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-one -octanone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4' -methyldimethylsulphide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentylbenzoic acid, benzil- β -methoxyethyl acetal, benzil dimethyl ketal, 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl O-benzoylbenzoate, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, methyl 4-dimethylthioxanthone, and mixtures thereof, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2, 4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide (cumene hydroperoxide), 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4, 5-bis (m-methoxyphenyl) -imidazole dimer, benzophenone, 2-chlorobenzophenone, 4 '-bisdimethylaminobenzophenone, 4' -bisdiethylaminobenzophenone, 4 '-dichlorobenzophenone, 2, 4' -diethylaminobenzophenone, 2-diethylthioxanthene, 2, 4-diethylthioxanthene, 2-methyl-2, 4-diethylthioxanthene, 2-methyl-ethyl-methyl-2-methyl-ethyl-methyl-2-isobutyl-benzene, 2-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-benzene, 3, 3-dimethyl-4-methoxybenzophenone, benzil, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropylketone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α -dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, 4-dimethylaminobenzoate pentyl ester, 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) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- [2- (furan-2-yl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- [2- (3, 4-Dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) 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-trichloromethyl-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 photopolymerization initiators may be used alone or in combination of 2 or more. When 2 or more kinds are combined, it is preferable to combine an oxime-based photopolymerization initiator with a photopolymerization initiator other than oxime-based ones.

Among the above, oxime-based photopolymerization initiators are particularly preferably used in view of sensitivity. Among oxime-based photopolymerization initiators, particularly preferred examples include O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl ] ethanone oxime, 1- [ 9-ethyl-6- (pyrrol-2-ylcarbonyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyloxime), and 1- [4- (phenylthio) ] -1, 2-octanedione-2- (O-benzoyloxime) (1,2-octanedione,1- [4- (phenylthio) -,2- (O-benzoyloxime) ].

Further, as the photopolymerization initiator, an oxime-based compound represented by the following formula (c1) is preferably used.

(R^c1Is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen group, a nitro group and a cyano group,

n1 is an integer of 0 to 4,

n2 is 0 or 1 and,

R^c2is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent,

R^c3is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )

In the formula (c1), R^c1The organic group is not particularly limited as long as it does not interfere with the object of the present invention, and can be appropriately selected from various organic groups. R^c1In the case of an organic group, preferable examples thereof include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group and an alkoxy groupAn alkylcarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, 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 naphthyloxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic 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, a halogen, a nitro group, a cyano group, and the like. When n1 is an integer of 2 to 4, R^c1May be the same or different. The number of carbon atoms of a substituent does not include the number of carbon atoms of a substituent which the substituent further has.

R^c1In the case of an alkyl group, the number of carbon atoms is preferably 1 to 20, and more preferably 1 to 6. In addition, R^c1When the alkyl group is used, it may be a straight chain or a branched chain. As R^c1Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl groups. In addition, R^c1In the case of an alkyl group, the carbon chain of the alkyl group may contain an ether bond (-O-). Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propoxyethoxyethyl group, and a methoxypropyl group.

R^c1In the case of an alkoxy group, the number of carbon atoms is preferably 1 to 20, and more preferably 1 to 6. In addition, R^c1When the alkoxy group is used, the alkoxy group may be a straight chain or a branched chain. As R^c1Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, a n-hexyloxy group, a n-heptyloxy groupN-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy and isodecyloxy. In addition, R^c1In the case of an alkoxy group, the carbon chain of the alkoxy group may contain an ether bond (-O-). Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propoxyethoxyethoxy, methoxypropoxy, and the like.

R^c1In the case of a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 to 10, and more preferably 3 to 6. As R^c1Specific examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As R^c1Specific examples of the cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

R^c1In the case of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 to 20, and more preferably 2 to 7. As R^c1Specific examples of the saturated aliphatic acyl group include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2-dimethylpropanoyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl and n-hexadecanoyl. As R^c1Specific examples of the saturated aliphatic acyloxy group include an acetoxy group, a propionyloxy group, a n-butyryloxy group, a 2-methylpropionyloxy group, a n-valeryloxy group, a2, 2-dimethylpropionyloxy group, a n-hexanoyloxy group, a n-heptanoyloxy group, a n-octanoyloxy group, a n-nonanoyloxy group, a n-decanoyloxy group, a n-undecanoyloxy group, a n-dodecanoyloxy group, a n-tridecanoyloxy group, a n-tetradecanoyloxy group, a n-pentadecanoyloxy group, and a n-hexadecanoyloxy group.

R^c1In the case of an alkoxycarbonyl group, the number of carbon atoms is preferably 2 to 20, and more preferably 2 to 7. As R^c1Specific examples of the alkoxycarbonyl group include methoxycarbonylAnd a phenyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, a n-hexyloxycarbonyl group, a n-heptyloxycarbonyl group, a n-octyloxycarbonyl group, an isooctyloxycarbonyl group, a sec-octyloxycarbonyl group, a tert-octyloxycarbonyl group, a n-nonyloxycarbonyl group, an isononyloxycarbonyl group, a n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

R^c1In the case of phenylalkyl, the number of carbon atoms is preferably 7 to 20, and more preferably 7 to 10. In addition, R^c1In the case of a naphthylalkyl group, the number of carbon atoms is preferably 11 to 20, and more preferably 11 to 14. As R^c1Specific examples of phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl. As R^c1Specific examples of the naphthylalkyl group include an α -naphthylmethyl group, a β -naphthylmethyl group, a2- (. alpha. -naphthyl) ethyl group and a2- (. beta. -naphthyl) ethyl group. R^c1When it is phenylalkyl or naphthylalkyl, R^c1May further have a substituent on the phenyl group or the naphthyl group.

R^c1When the heterocyclic group is a 5-or 6-membered monocyclic ring containing 1 or more N, S, O atoms, or a heterocyclic group in which the monocyclic rings are fused with each other or the monocyclic ring is fused with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline (cinnoline), quinoxaline and the like. R^c1When it is a heterocyclic group, the heterocyclic group may further have a substituent.

R^c1When the amino group is substituted with 1 or 2 organic groups, preferable 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 a2 to c20, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzoyl group, a substituted or unsubstituted phenylalkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted naphthoyl group, a substituted or unsubstituted naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclic group or the like. Specific examples of these preferred organic groups and R^c1The same is true. Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-valerylamino, n-hexanoylamino, n-heptanoylamino, n-octanoylamino, n-decanoylamino, benzoylamino, α -naphthoylamino and β -naphthoylamino.

R^c1When the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, halogen, nitro, cyano and the like. R^c1When the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a substituent, the number of the substituent is not limited within the range not interfering with the object of the present invention, and is preferably 1 to 4. R^c1When the phenyl group, naphthyl group and heterocyclic group contained in (1) have a plurality of substituents, the plurality of substituents may be the same or different.

R^c1Among them, from the viewpoint of chemical stability, small steric hindrance, and easy synthesis of oxime ester compounds, a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a saturated aliphatic acyl group having 2 to 7 carbon atoms is preferable, and a carbon atom is more preferableThe alkyl group having a sub-number of 1 to 6 is particularly preferably a methyl group.

For R^c1When the bonded phenyl group is a position of a chemical bond between the phenyl group and the main skeleton of the oxime ester compound as the 1-position and the methyl group as the 2-position, R is^c1The position bonded to the phenyl group is preferably the 4-or 5-position, more preferably the 5-position. N1 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

R^c2Is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent. In addition, R^c2When the carbazolyl group is optionally substituted, the nitrogen atom on the carbazolyl group may be substituted by an alkyl group having 1 to 6 carbon atoms.

R^c2In (3), the substituent group of the phenyl group or the carbazolyl group is not particularly limited insofar as it does not interfere with the object of the present invention. Examples of the preferable substituent which may be contained in a carbon atom of the phenyl group or the carbazolyl group include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, Naphthoyloxy which may have a substituent, naphthylalkyl which may have a substituent and has 11 to 20 carbon atoms, heterocyclic group which may have a substituent, heterocyclic carbonyl which may have a substituent, amino substituted by 1 or 2 organic groups, morpholin-1-yl and piperazin-1-yl, halogen, nitro, cyano and the like.

R^c2In the case of the carbazolyl group, examples of preferable substituents which may be contained in the nitrogen atom of the carbazolyl group include an alkyl group having 1 to 20 carbon atoms and an alkyl group having 3 to 10 carbon atomsThe cycloalkyl group, the saturated aliphatic acyl group having 2 to 20 carbon atoms, the alkoxycarbonyl group having 2 to 20 carbon atoms, the phenyl group which may have a substituent, the benzoyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, the naphthyl group which may have a substituent, the naphthoyl group which may have a substituent, the naphthyloxycarbonyl group which may have a substituent, the naphthylalkyl group which may have 11 to 20 carbon atoms which may have a substituent, the heterocyclic group which may have a substituent, the heterocyclic carbonyl group which may have a substituent, and the like. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent which may be contained in the phenyl group or the carbazolyl group include alkyl group, alkoxy group, cycloalkyl group, cycloalkoxy group, saturated aliphatic acyl group, alkoxycarbonyl group, saturated aliphatic acyloxy group, phenylalkyl group which may be substituted, naphthylalkyl group which may be substituted, heterocyclic group which may be substituted, and amino group substituted with 1 or 2 organic groups, and R^c1The same is true.

R^c2In the above formula, when the phenyl group, naphthyl group and heterocyclic group contained in the substituent group of the phenyl group or carbazolyl group further have a substituent group, examples of the substituent 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; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a 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; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl; piperazin-1-yl; halogen; a nitro group; a cyano group. When the phenyl group, naphthyl group and heterocyclic group included in the substituent group of the phenyl group or carbazolyl group further have a substituent group, the number of the substituent group is not limited within the range not interfering with the object of the present invention, and is preferably 1 to 4. When the phenyl group, naphthyl group and heterocyclic group have plural substituents, the plural substituents may be the same or differentThe same is true.

R^c2Among them, from the viewpoint of easily obtaining a photopolymerization initiator excellent in sensitivity, a group represented by the following formula (c2) or (c3) is preferable, a group represented by the following formula (c2) is more preferable, and a group represented by the following formula (c2) in which a is S is particularly preferable.

(R^c4Is 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. )

(R^c5And R^c6Each a monovalent organic group. )

R in the formula (c2)^c4In the case of an organic group, it may be selected from various organic groups within a range not interfering with the object of the present invention. As R in formula (c2)^c4Preferable examples of the 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; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a 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; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl; piperazin-1-yl; halogen; a nitro group; a cyano group.

R^c4Among them, benzoyl is preferred; a 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; nitro, more preferably benzoyl; a naphthoyl group; 2-methylphenylcarbonyl; 4- (piperazin-1-yl) phenylcarbonyl; 4- (phenyl) phenylcarbonyl。

In the formula (c2), n3 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When n3 is 1, R^c4Is preferably relative to R^c4The chemical bond of the bonded phenyl group to the oxygen atom or the sulfur atom is para.

R in the formula (c3) is not particularly limited in the range not interfering with the object of the present invention^c5Can be selected from various organic groups. As R^c5Preferable examples of (3) include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, and a heterocyclic carbonyl group which may have a substituent.

R^c5Among them, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

R in the formula (c3)^c6The organic group is not particularly limited as long as the object of the present invention is not impaired, and may be selected from various organic groups. As to suitability as R^c6Specific examples of the group (b) include an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group and an optionally substituted heterocyclic group. Of these groups, as R^c6More preferred is a phenyl group which may have a substituent, and particularly preferred is a 2-methylphenyl group.

R^c4、R^c5Or R^c6When the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a heterocyclic group having a ring structureMonoalkylamino group having an alkyl group of a number of 1 to 6, dialkylamino group having an alkyl group of a carbon number of 1 to 6, morpholin-1-yl, piperazin-1-yl, halogen, nitro group, cyano group, and the like. R^c4、R^c5Or R^c6When the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a substituent, the number of the substituent is not limited within the range not interfering with the object of the present invention, and is preferably 1 to 4. R^c4、R^c5Or R^c6When the phenyl group, naphthyl group and heterocyclic group included in (1) have a plurality of substituents, the plurality of substituents may be the same or different.

R in the formula (c1)^c3Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. As R^c3Preferably methyl or ethyl, more preferably methyl.

The oxime ester compound represented by the formula (c1) can be synthesized, for example, according to the following synthesis scheme 1 when n2 is 0. Specifically, an aromatic compound represented by the following formula (c1-1) is acylated using a halogenated carbonyl compound represented by the following formula (c1-2) by Friedel-Crafts reaction to obtain a ketone compound represented by the following formula (c1-3), the obtained ketone compound (c1-3) is oximated with hydroxylamine to obtain an oxime compound represented by the following formula (c1-4), and then the hydroxyl group in the oxime compound represented by the following formula (c1-4) is acylated to obtain an oxime ester compound represented by the following formula (c 1-7). As the acylating agent, it is preferable to use an acid anhydride ((R) represented by the following formula (c1-5)^c3CO)₂O) or an acid halide (R) represented by the following formula (c1-6)^c3COHal, Hal is halogen. ). In the formula (c1-2), Hal is halogen, and R in the formulae (c1-1), (c1-2), (c1-3), (c1-4) and (c1-7)^c1、R^c2、R^c3And n1 are the same as in formula (c 1).

< synthetic route 1>

The oxime ester compound represented by the formula (c1) wherein n2 is 1 can be synthesized, for example, according to the following synthesis scheme 2. In particular, in the presence of hydrochloric acidThen, a ketone compound represented by the following formula (c2-1) is reacted with a nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following formula (c2-2) to obtain a ketoxime compound represented by the following formula (c2-3), and then, a hydroxyl group in the ketoxime compound represented by the following formula (c2-3) is acylated to obtain an oxime ester compound represented by the following formula (c 2-6). As the acylating agent, it is preferable to use an acid anhydride ((R) represented by the following formula (c2-4)^c3CO)₂O) or an acid halide (R) represented by the following formula (c2-5)^c3COHal, Hal is halogen). In the following formulae (c2-1), (c2-3), (c2-4), (c2-5) and (c2-6), R is^c1、R^c2、R^c3And n1 are the same as in formula (c 1).

< synthetic route 2>

In addition, for the oxime ester compound represented by the formula (c1), when n2 is 1, R^c1Is methyl and is opposite to the bond to R^c1Methyl, R on the bonded benzene ring^c1In the case where the bond is in the para-position, it can be synthesized, for example, by oximation and acylation of a compound represented by the following formula (c2-7) in the same manner as in the synthesis scheme 1. In the following formula (c2-7), R^c2The same as in formula (c 1).

Particularly preferred oxime ester compounds represented by the formula (c1) include PI-1 to PI-42.

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

(R^c7Is a hydrogen atom, a nitro group or a monovalent organic group, R^c8And R^c9Each is a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent or a hydrogen atom, R^c8And R^c9May be bonded to each other to form a ring, R^c10Is a monovalent organic radical, R^c11Is 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 of 0 to 4, and n5 is 0 or 1. )

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

(R^c7、R^c8、R^c9、R^c10N4 and n5 are the same as in formula (c 4). )

In the formulae (c4) and (c5)，R^c7Is a hydrogen atom, a nitro group or a monovalent organic group. R^c7To the fluorene ring in formula (c4) with- (CO)_n56-membered aromatic rings different from the 6-membered aromatic ring to which the group represented by (A) is bonded. In the formula (c4), R^c7The bonding position to the fluorene ring is not particularly limited. The compound represented by the formula (c4) has 1 or more R^c7In this case, it is preferable that 1 or more R's are contained in order to facilitate the synthesis of the compound represented by the formula (c4)^c71 in (b) is bonded to the 2-position in the fluorene ring. R^c7When there are plural, plural R^c7May be the same or different.

R^c7When it is an organic group, R^c7The organic group is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. As R^c7Preferable examples of the organic group 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, an optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy group, phenylalkyl which may have a substituent, naphthyl which may have a substituent, naphthyloxy which may have a substituent, naphthoyl which may have a substituent, naphthyloxycarbonyl which may have a substituent, naphthoyloxy which may have a substituent, naphthylalkyl which may have a substituent, heterocyclic group which may have a substituent, heterocyclic carbonyl which may have a substituent, amino substituted with 1 or 2 organic groups, morpholin-1-yl and piperazin-1-yl, and the like.

R^c7In the case of an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 6. In addition, R^c7When the alkyl group is used, it may be a straight chain or a branched chain. As R^c7Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl groups. In addition, R^c7When it is an alkyl group, of the alkyl groupThe carbon chain may contain an ether bond (-O-). Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propoxyethoxyethyl group, a methoxypropyl group, and the like.

R^c7In the case of an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 6. In addition, R^c7When the alkoxy group is used, the alkoxy group may be a straight chain or a branched chain. As R^c7Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy. In addition, R^c7In the case of an alkoxy group, the carbon chain of the alkoxy group may contain an ether bond (-O-). Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propoxyethoxyethoxy, methoxypropoxy, and the like.

R^c7When the alkyl group is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 to 10, more preferably 3 to 6. As R^c7Specific examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As R^c7Specific examples of the cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

R^c7In the case of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. As R^c7Specific examples of the saturated aliphatic acyl group include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2-dimethylpropanoyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl and n-undecanoylN-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl and n-hexadecanoyl, etc. As R^c7Specific examples of the saturated aliphatic acyloxy group include an acetoxy group, a propionyloxy group, a n-butyryloxy group, a 2-methylpropionyloxy group, a n-valeryloxy group, a2, 2-dimethylpropionyloxy group, a n-hexanoyloxy group, a n-heptanoyloxy group, a n-octanoyloxy group, a n-nonanoyloxy group, a n-decanoyloxy group, a n-undecanoyloxy group, a n-dodecanoyloxy group, a n-tridecanoyloxy group, a n-tetradecanoyloxy group, a n-pentadecanoyloxy group, and a n-hexadecanoyloxy group.

R^c7In the case of an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 20, more preferably 2 to 7. As R^c7Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, a n-hexyloxycarbonyl group, a n-heptyloxycarbonyl group, a n-octyloxycarbonyl group, an isooctyloxycarbonyl group, a sec-octyloxycarbonyl group, a tert-octyloxycarbonyl group, a n-nonyloxycarbonyl group, an isononyloxycarbonyl group, a n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

R^c7In the case of phenylalkyl, the number of carbon atoms in phenylalkyl is preferably 7 to 20, more preferably 7 to 10. In addition, R^c7In the case of a naphthylalkyl group, the number of carbon atoms in the naphthylalkyl group is preferably 11 to 20, more preferably 11 to 14. As R^c7Specific examples of phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl. As R^c7Specific examples of the naphthylalkyl group include an α -naphthylmethyl group, a β -naphthylmethyl group, a2- (. alpha. -naphthyl) ethyl group and a2- (. beta. -naphthyl) ethyl group. R^c7When it is phenylalkyl or naphthylalkyl, R^c7The phenyl group or naphthyl group may further have a substituent.

R^c7When it is a heterocyclic group, the heterocyclic group is a 5-or 6-membered monocyclic ring containing 1 or more N, S, O atoms, or a heterocyclic ring in which the monocyclic rings are fused with each other or the monocyclic ring is fused with a benzene ringAnd (4) a base. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran, and the like. R^c7When it is a heterocyclic group, the heterocyclic group may further have a substituent.

R^c7When it is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group and R^c7The same applies to heterocyclic groups.

R^c7In the case of an amino group substituted with 1 or 2 organic groups, preferable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group and the like. Specific examples of these preferred organic groups and R^c7The same is true. Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-valerylamino, n-hexanoylamino, n-heptanoylamino, n-octanoylamino, n-decanoylamino, benzoylamino, α -naphthoylamino and β -naphthoylamino.

R^c7The phenyl group contained in (A),When the naphthyl group and the heterocyclic group further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group and the like. R^c7When the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a substituent, the number of the substituent is not limited within the range not interfering with the object of the present invention, and is preferably 1 to 4. R^c7When the phenyl group, naphthyl group and heterocyclic group contained in (1) have a plurality of substituents, the plurality of substituents may be the same or different.

In the above-described groups, R^c7Is nitro or R^c12The group represented by-CO-is preferred because the sensitivity tends to be increased. R^c12The organic group is not particularly limited as long as the object of the present invention is not impaired, and may be selected from various organic groups. As to suitability as R^c12Examples of the group (b) include an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group and an optionally substituted heterocyclic group. Of these groups, as R^c12Particularly preferred are 2-methylphenyl, thiophen-2-yl and α -naphthyl.

In addition, R^c7The hydrogen atom is preferred because it tends to improve transparency. If R is to be noted^c7Is a hydrogen atom and R^c10The group represented by the formula (c4b) described later tends to have better transparency.

In the formula (c4), R^c8And R^c9Each is a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R^c8And R^c9May be bonded to each other to form a ring. Of these groups, as R^c8And R^c9Preferably, the alkyl group is a chain alkyl group which may have a substituent. R^c8And R^c9When the alkyl group is a linear alkyl group which may have a substituent, the linear alkyl group may be a linear alkyl group or a linear alkyl groupIs a branched alkyl group.

R^c8And R^c9In the case of a chain alkyl group having no 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. As R^c8And R^c9Specific examples of the chain alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl groups. In addition, R^c8And R^c9In the case of an alkyl group, the carbon chain of the alkyl group may contain an ether bond (-O-). Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propoxyethoxyethyl group, a methoxypropyl group, and the like.

R^c8And R^c9In the case of a chain alkyl group 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 of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably straight.

The substituent that the alkyl group may have is not particularly limited within a range that does not interfere with the object of the present invention. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, fluorine atom, chlorine atom and bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group. As specific examples of cycloalkyl, with R^c7The same applies to the preferred cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, and the like. As specific examples of heterocyclic groups, with R^c7The same applies to the preferred examples of heterocyclic groups. R^c7In the case of an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. Of alkoxy groups contained in alkoxycarbonyl groupsThe number of carbon atoms is preferably 1 to 10, more preferably 1 to 6.

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

R^c8And R^c9In the case of a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. R^c8And R^c9When it is a cyclic organic group, the cyclic organic group may have a substituent and R^c8And R^c9The same applies to a chain alkyl group.

R^c8And R^c9In the case of an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably: a phenyl group, a group in which a plurality of benzene rings are bonded via a carbon-carbon bond, or a group in which a plurality of benzene rings are condensed. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or fusing a plurality of benzene rings, the number of the benzene rings contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Preferred specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, and the like.

R^c8And R^c9In the case of the alicyclic hydrocarbon group, the alicyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20, and more preferably 3 to 10. Examples of the monocyclic cyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl, and adamantyl.

R^c8And R^c9When the heterocyclic group is a 5-or 6-membered monocyclic ring containing 1 or more N, S, O atoms, or a heterocyclic group in which the monocyclic rings are fused with each other or the monocyclic ring is fused with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. The heterocyclic group may be aromaticThe group (heteroaryl) may also be a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran, and the like.

R^c8And R^c9May be bonded to each other to form a ring. Comprising R^c8And R^c9The radical of the ring formed is preferably cycloalkylene (cycloalkylidene group). R^c8And R^c9When the cycloalkylene group is bonded to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a 5-to 6-membered ring, and more preferably a 5-membered ring.

R^c8And R^c9When the group to which the bond is formed is a cycloalkylene group, the cycloalkylene group may be fused with 1 or more other rings. Examples of the ring which may be fused with a cycloalkylene 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, a pyrazine ring, a pyrimidine ring, and the like.

R as described above^c8And R^c9Examples of the preferable group in (1) include the group of the formula (A)¹-A²The group shown. In the formula, A¹Is a straight-chain alkylene radical, with respect to A²Examples thereof include an alkoxy group, a cyano group, a halogen atom, a haloalkyl group, a cyclic organic group and an alkoxycarbonyl group.

A¹The number of carbon atoms of the linear alkylene group(s) is preferably 1 to 10, more preferably 1 to 6. A. the²In the case of an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 to 10, more preferably 1 to 6. A. the²In the case of 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. A. the²When it is haloalkyl, haloThe halogen atom contained in the alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom, a chlorine atom or a bromine atom. The haloalkyl group may be linear or branched, and is preferably linear. A. the²Examples of cyclic organic radicals and R^c8And R^c9The cyclic organic group as a substituent is the same. A. the²Examples of alkoxycarbonyl radicals and R when alkoxycarbonyl radicals are present^c8And R^c9The same applies to the alkoxycarbonyl group as a substituent.

As R^c8And R^c9Preferred specific examples of (3) include: alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; alkoxyalkyl groups such as 2-methoxyethyl, 3-methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8-methoxy-n-octyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy-n-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy-n-heptyl, and 8-ethoxy-n-octyl; cyanoalkyl groups such as 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl, 6-cyano-n-hexyl, 7-cyano-n-heptyl, and 8-cyano-n-octyl; phenylalkyl groups such as 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl and 8-phenyl-n-octyl; cycloalkylalkyl groups such as 2-cyclohexylethyl, 3-cyclohexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopentyl-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; 2-methoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl, 6-methoxycarbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, 8-methoxycarbonyl-n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n-propyl, 4-ethoxycarbonyl-n-butyl, 5-ethoxycarbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl and 8-ethylAlkoxycarbonyl alkyl groups such as oxycarbonyl n-octyl group; haloalkyl groups such as 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl, 3,3, 3-trifluoropropyl, and 3,3,4,4,5,5, 5-heptafluoro-n-pentyl.

As R^c8And R^c9Preferred groups among the above are: ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl, 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3, 3-trifluoropropyl and 3,3,4,4,5,5, 5-heptafluoro-n-pentyl.

As R^c10Examples of preferred organic radicals of (1) with R^c7Similarly, there may be mentioned alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acyloxy, phenyl which may have a substituent, phenoxy which may have a substituent, benzoyl which may have a substituent, phenoxycarbonyl which may have a substituent, benzoyloxy which may have a substituent, phenylalkyl which may have a substituent, naphthyl which may have a substituent, naphthyloxy which may have a substituent, naphthoyl which may have a substituent, naphthyloxycarbonyl which may have a substituent, naphthoyloxy which may have a substituent, naphthylalkyl which may have a substituent, heterocyclic group which may have a substituent, heterocyclic carbonyl which may have a substituent, amino substituted by 1 or 2 organic groups, morpholin-1-yl, piperazin-1-yl and the like. Specific examples of these groups and p-R^c7The same applies to the description. In addition, as R^c10Also preferred are cycloalkylalkyl groups, phenoxyalkyl groups which may have substituents on the aromatic rings, and phenylthioalkyl groups which may have substituents on the aromatic rings. Phenoxyalkyl and phenylthioalkyl substituents and R^c7The same applies to the substituents which the phenyl group may have.

In the organic radical, as R^c10Preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a cycloalkylalkyl group, a phenylthioalkyl group which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2- (4-chlorophenylthio) ethyl group is preferable.

In addition, as R^c10Further preferred is-A³-CO-O-A⁴The group shown. A. the³Is a divalent organic group, preferably a divalent hydrocarbon group, more preferably an alkylene group. A. the⁴Is a monovalent organic group, preferably a monovalent hydrocarbon group.

A³In the case of an alkylene group, the alkylene group may be linear or branched, and is preferably linear. A. the³In the case of an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

As A⁴Preferred examples of the alkyl group include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. As A⁴Preferable specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, α -naphthylmethyl and β -naphthylmethyl.

As a³-CO-O-A⁴Preferred specific examples of the group include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl, 2-n-butoxycarbonylethyl, 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methylcarbonylethylOxycarbonyl-n-propyl group, 3-ethoxycarbonyl-n-propyl group, 3-n-propoxycarbonyl-n-propyl group, 3-n-butoxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group, 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, 3-phenoxycarbonyl-n-propyl group and the like.

Above pair R^c10Has been described as R^c10Preferably, the group is represented by the following formula (c4a) or (c4 b).

(in the formulae (c4a) and (c4b), R^c13And R^c14Each is an organic group, n6 is an integer of 0 to 4, R^c13And R^c14When present in adjacent positions on the phenyl ring, R^c13And R^c14Can form a ring by bonding with each other, 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^c15Is an organic group. )

With respect to R in the formula (c4a)^c13And R^c14Examples of organic radicals of (1), with R^c7The same is true. As R^c13Preferably an alkyl group or a phenyl group. R^c13When the alkyl group is used, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. Namely, R^c13Most preferred is methyl. R^c13And R^c14When the bond forms a ring, the ring may be an aromatic ring or an aliphatic ring. As R^c13And R^c14Preferred examples of the group represented by the formula (c4a) having a ring formed thereon include naphthalen-1-yl, 1,2,3, 4-tetrahydronaphthalen-5-yl and the like. In the formula (c4a), n6 is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the above formula (c4b), R^c15Is an organic group. Examples of the organic group include those related to R^c7And the organic groups illustrated are the same. Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. As R^c15Preferably, methyl group,Ethyl, propyl, isopropyl, butyl, etc., among which methyl 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, and particularly preferably 0. In the formula (c4b), n7 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

In the formula (c4), R^c11Is 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 R^c11The substituent which may be present in the case of an alkyl group is preferably a phenyl group, a naphthyl group or the like. In addition, as R^c7The substituent which may be contained in the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom or the like.

In the formula (c4), R is^c11Examples thereof include preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group and naphthyl group, and among them, more preferably a methyl group or a phenyl group.

The compound represented by the formula (c4) may be prepared by including the oximino group (c5) contained in the compound represented by the formula (c5)>C ═ N-OH) to compounds consisting of>C＝N-O-COR^c11The oxime ester group shown above. R^c11And R in the formula (c4)^c11The same is true.

Oximino (b)>C ═ N-OH) toward>C＝N-O-COR^c11The conversion of the oxime ester group can be carried out by reacting a compound represented by the above formula (c5) with an acylating agent.

As a provision by-COR^c11As the acylating agent for the acyl group, there may be mentioned (R)^c11CO)₂Acid anhydride represented by O, R^c11Acid halides represented by COHal (Hal is a halogen atom).

The compound represented by the general formula (c4), wherein n5 is 0, can be synthesized, for example, according to the following synthesis scheme 3. In Synthesis route 3, a fluorene derivative represented by the following formula (c3-1) is used as a starting material. R^c7In the case of a nitro group or a monovalent organic group, the fluorene derivative represented by the formula (c3-1)For example, R can be substituted at the 9-position by using a known method^c8And R^c9Introduction of substituent R into substituted fluorene derivative^c7And obtaining the compound. For 9 bits by R^c8And R^c9Substituted fluorene derivatives, e.g. R^c8And R^c9When it is an alkyl group, it can be obtained as follows: as described in Japanese patent application laid-open No. H06-234668, fluorene is reacted with an alkylating agent in an aprotic polar organic solvent in the presence of an alkali metal hydroxide. Furthermore, 9-alkyl-substituted fluorenes can be obtained by adding an alkylating agent such as a halogenated alkyl group, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide to an organic solvent solution of the fluorene to carry out an alkylation reaction.

Introduction of a group represented by the formula (c3-1) into a fluorene derivative by Friedel-crafts acylation^c10The acyl group represented by the formula (c3-3) gives a fluorene derivative. For introducing compounds consisting of-CO-R^c10The acylating agent of the acyl group may be a halocarbonyl compound or an acid anhydride. As the acylating agent, a halocarbonyl compound represented by the formula (c3-2) is preferable. In the formula (c3-2), Hal is a halogen atom. The position of the fluorene ring at which the acyl group is introduced can be selected by appropriately changing the conditions of the Friedel-crafts reaction or protecting and deprotecting the position other than the position at which acylation is carried out.

Then, the resulting fluorene derivative represented by formula (c3-3) is subjected to reaction with-CO-R^c10Conversion of the group represented by-C (═ N-OH) -R^c10The group represented by (c) to give an oxime compound represented by the formula (c 3-4). Will consist of-CO-R^c10Conversion of the group represented by-C (═ N-OH) -R^c10The method of the group represented is not particularly limited, but oximation by hydroxylamine is preferable. An oxime compound of the formula (c3-4) and an acid anhydride ((R) represented by the following formula (c3-5)^c11CO)₂O) or an acid halide (R) represented by the following formula (c3-6)^c11COHal, Hal is a halogen atom. ) The reaction was carried out to obtain a compound represented by the following formula (c 3-7).

The formulae (c3-1), (c3-2), (c3-3) and (c3-4)In (c3-5), (c3-6) and (c3-7), R^c7、R^c8、R^c9、R^c10And R^c11The same as in formula (c 4).

In addition, in synthetic route 3, each of the formula (c3-2), the formula (c3-3) and the formula (c3-4) contains R^c10May be the same or different. That is, in the synthesis process shown in synthetic route 3, R in the formulae (c3-2), (c3-3) and (c3-4)^c10Chemical modifications are acceptable. Examples of the chemical modification include esterification, etherification, acylation, amidation, halogenation, and substitution of a hydrogen atom in an amino group with an organic group. R^c10Acceptable chemical modifications are not limited to these.

< Synthesis route 3>

When n5 is 1, the compound represented by the formula (c4) can be synthesized, for example, according to the following synthesis scheme 4. In Synthesis route 4, a fluorene derivative represented by the following formula (c4-1) is used as a starting material. The fluorene derivative represented by formula (c4-1) can be prepared by introducing-CO-CH into a compound represented by formula (c3-1) by Friedel-crafts reaction in the same manner as in Synthesis route 3₂-R^c10The acyl group shown. As the acylating agent, preferred is a compound represented by the formula (c 3-8): Hal-CO-CH₂-R^c10The carboxylic acid halide is shown. Next, the compound represented by the formula (c4-1) wherein R is present^c10Oximation of the methylene group with the carbonyl group is carried out to obtain a ketoxime compound represented by the following formula (c 4-3). The method for oximation of methylene is not particularly limited, and is preferably a method in which nitrite (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following formula (c4-2) is reacted in the presence of hydrochloric acid. Next, a ketoxime compound represented by the following formula (c4-3) and an acid anhydride represented by the following formula (c4-4) ((R)^c11CO)₂O) or an acid halide (R) represented by the following formula (c4-5)^c11COHal, Hal is a halogen atom. ) The reaction was carried out to obtain a compound represented by the following formula (c 4-6). In addition, the following formulas (c4-1), (c4-3) In (c4-4), (c4-5) and (c4-6), R^c7、R^c8、R^c9、R^c10And R^c11The same as in formula (c 4).

When n5 is 1, the following tendency exists: foreign matter generated in a pattern formed using the photosensitive resin composition containing the compound represented by formula (c4) can be further reduced.

In addition, in synthetic route 4, each of the formula (c3-8), the formula (c4-1) and the formula (c4-3) contains R^c10May be the same or different. That is, in the synthesis process shown in synthetic route 4, R in the formulae (c3-8), (c4-1) and (c4-3)^c10Chemical modifications are acceptable. Examples of the chemical modification include esterification, etherification, acylation, amidation, halogenation, and substitution of a hydrogen atom in an amino group with an organic group. R^c10Acceptable chemical modifications are not limited to these.

< Synthesis route 4>

Preferable specific examples of the compound represented by the formula (c4) include the following PI-43 to PI-82.

The content of the photopolymerization initiator (C) is preferably 0.5 to 20 parts by mass per 100 parts by mass of the solid components of the photosensitive resin composition. By setting the above range, a photosensitive resin composition having both good coatability and curability can be easily prepared.

[ D ] pigment ]

The photosensitive resin composition may contain the pigment (D) in addition to the pigment (D). The photosensitive resin composition containing no (D) pigment is useful for forming a transparent insulating film, for example, because it can form a transparent cured film. The photosensitive resin composition containing the pigment (D) can form a cured film colored in various hues in accordance with the hue of the pigment (D), and is useful for forming a color filter or a black columnar spacer.

The pigment (D) contained in the photosensitive resin composition is not particularly limited. The use of a dye together with the (D) pigment is also preferred.

As The Pigment (D), for example, a compound classified as a Pigment (Pigment) in The color index (C.I.; issued by The Society of Dyers and Colourists Co., Ltd.) is preferably used, and specifically, a compound having a color index (C.I.) number as described below is preferably used.

Examples of a yellow pigment that can be suitably used include c.i. pigment yellow 1 (hereinafter, also referred to as "c.i. pigment yellow" simply as a reference), 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.

Examples of orange pigments that can be suitably used include c.i. pigment orange 1 (hereinafter, also referred to as "c.i. pigment orange", only as reference numeral), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, and 73.

Examples of violet pigments that can be suitably used include c.i. pigment violet 1 (hereinafter, also referred to as "c.i. pigment violet" simply as a reference), 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, also referred to as "c.i. pigment red" only as a reference), 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 and 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, 217, 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, also referred to as "c.i. pigment blue" and simply referred to as "c.i. pigment blue"), 2, 15, and 15: 3. 15: 4. 15: 6. 16, 22, 60, 64 and 66.

Examples of pigments having other color tones than those described above which can be suitably used include green pigments such as c.i. pigment green 7, c.i. pigment green 36 and c.i. pigment green 37, brown pigments such as c.i. pigment brown 23, c.i. pigment brown 25, c.i. pigment brown 26 and c.i. pigment brown 28, and black pigments such as c.i. pigment black 1 and c.i. pigment black 7.

In addition, (D) pigments are also preferred as opacifiers. By using a photosensitive resin composition containing a light-shading agent as the pigment (D), a black columnar spacer, a black matrix, and the like having desirable characteristics can be formed. When the pigment (D) is used as a light-shading agent, a black pigment or a violet pigment is preferably used as the light-shading agent. Examples of the black pigment and violet pigment include various pigments, whether organic or inorganic, such as carbon black, perylene pigment, titanium black, metal oxides, composite oxides, metal sulfides, metal sulfates, and metal carbonates of copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver. Among them, carbon black having a high light-shielding property is preferably used.

As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black (lampblack) can be used, and channel black having excellent light-shielding properties is preferably used. In addition, carbon black coated with a resin may also be used.

Carbon black subjected to treatment for introducing an acidic group is also preferable. The acidic group introduced into the carbon black is a functional group showing acidity based on the definition of bronsted. Specific examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The acidic groups introduced into the carbon black may form salts. The cation forming a salt with an acidic group is not particularly limited insofar as it does not interfere with the object of the present invention. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions, and the like, and alkali metal ions such as sodium ions, potassium ions, and lithium ions, and ammonium ions are preferable.

Among the carbon blacks subjected to the treatment for introducing an acidic group described above, carbon blacks having 1 or more functional groups selected from the group consisting of a carboxylic acid group, a carboxylate group, a sulfonic acid group and a sulfonate group are preferable in terms of low relative permittivity of the light-shielding cured film formed using the photosensitive resin composition.

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

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

2) A method for 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 etherification.

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

5) A method of conducting Friedel-crafts reaction on carbon black using an organic compound having a halocarbonyl group and an acid group protected by a protecting group, followed by deprotection.

Among the above methods, method 2) is preferred in view of ease of treatment for introducing an acidic group and safety. As the organic compound having an amino group and an acidic group used in the method 2), a compound in which an amino group and an acidic group are bonded to an aromatic group is preferable. Examples of such a compound include aminobenzenesulfonic acid such as sulfanilic acid and aminobenzoic acid such as 4-aminobenzoic acid.

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

The carbon black having an acid group introduced thereto may be coated with a resin.

When a photosensitive resin composition containing resin-coated carbon black is used, a light-shielding cured film having excellent light-shielding properties and insulating properties and low surface reflectance can be easily formed. The coating treatment with the resin does not particularly adversely affect the dielectric constant of the light-shielding cured film formed using the photosensitive resin composition. Examples of the resin that can be used for coating carbon black include thermosetting resins such as phenol resins, melamine resins, xylene resins, diallyl phthalate resins, glyphosate (acetal) resins, epoxy resins, and alkylbenzene resins; thermoplastic resins such as polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polysulfone, poly (p-phenylene terephthalamide), polyamideimide, polyimide, polyaminobismaleimide, polyethersulfonepolyphenylenesulfone, polyarylate, and polyetheretherketone. The amount of resin coating on the carbon black is preferably 1 to 30% by mass based on the total mass of the carbon black and the resin.

Further, as the light-shading agent, perylene pigments are also preferable. 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). Of commercially available products, perylene pigments such as K0084 and K0086, pigment Black 21, 30, 31, 32, 33 and 34, manufactured by BASF corporation, are preferably used.

In the formula (d-1), R^d1And R^d2Each independently represents an alkylene group having 1 to 3 carbon atoms, R^d3And R^d4Each independently represents a hydrogen atom, a hydroxyl group, a methoxy group or an acetyl group.

In the formula (d-2), R^d5And R^d6Each independently represents an alkylene group having 1 to 7 carbon atoms.

In the formula (d-3), R^d7And R^d8Each independently represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, and may contain a hetero atom N, O, S or P. R^d7And R^d8In the case of an alkyl group, the alkyl group 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) can be synthesized, for example, by the methods described in Japanese patent laid-open Nos. 62-1753 and 63-26784. Namely, perylene-3, 5,9, 10-tetracarboxylic acid or dianhydride thereof and amine are used as raw materials, and are heated and reacted in water or an organic solvent. Then, the obtained crude product is reprecipitated in sulfuric acid, or recrystallized in water, an organic solvent or a mixed solvent thereof, whereby the target product can be obtained.

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

The light-shading agent may contain not only the above black pigment and/or violet pigment but also pigments having a hue of red, blue, green, yellow, etc., for the purpose of adjusting the hue, etc. The coloring matter of other color tones than the black coloring matter and the violet coloring matter can be appropriately selected from known coloring matters. For example, as the coloring matter of other color tones than the black pigment and the violet pigment, the above-mentioned various pigments can be used. The amount of the pigment of a color tone other than the black pigment and the violet pigment used is preferably 15% by mass or less, and more preferably 10% by mass or less, based on the total mass of the light-shading agent.

In order to uniformly disperse the pigment (D) in the photosensitive resin composition, a dispersant may be further used. As such a dispersant, a polyethyleneimine-based, urethane-based, or acrylic resin-based polymer dispersant is preferably used. In particular, when carbon black is used as the pigment (D), an acrylic resin-based dispersant is preferably used as the dispersant.

The inorganic pigment and the organic pigment may be used singly or in combination of 2 or more, and when used in combination, the organic pigment is preferably used in an amount of 10 to 80% by mass, more preferably 20 to 40% by mass, based on the total mass of the inorganic pigment and the organic pigment.

The amount of the pigment (D) used in the photosensitive resin composition may be appropriately selected within a range not interfering with the object of the present invention, and is typically preferably 5 to 70% by mass, more preferably 25 to 60% by mass, based on the mass of the solid components in the photosensitive resin composition.

Preferably, after the (D) pigment is dispersed at an appropriate concentration using a dispersant to prepare a dispersion, the dispersion is added to the photosensitive resin composition.

In the case where the pigment (D) is used as the colorant in the conventional photosensitive resin composition, the pigment particles may aggregate and the photosensitive resin composition may thicken depending on the type of the solvent (S).

However, when the photosensitive resin composition contains a compound containing an aromatic hydrocarbon ring and an ester bond, which will be described later, as the (S) solvent, the photosensitive resin composition can be inhibited from thickening during storage and from aggregating pigment particles.

< S solvent >

The photosensitive resin composition contains a (S) solvent. The (S) solvent comprises a combination of (L) a low-boiling solvent having a boiling point of less than 180 ℃ under atmospheric pressure and (H) a high-boiling solvent having a boiling point of 180 ℃ or higher and 300 ℃ or lower under atmospheric pressure.

Hereinafter, (L) the low boiling point solvent and (H) the high boiling point solvent will be described.

((L) Low boiling solvent)

The (S) solvent comprises (L) a low boiling point solvent having a boiling point of less than 180 ℃ at atmospheric pressure.

By containing a predetermined amount of the (L) low boiling point solvent having a boiling point within the above range in the (S) solvent, the (S) solvent can be volatilized at an appropriate speed when the photosensitive resin composition is applied to a substrate to form a coating film, and the residual amount of the (S) solvent in the coating film can be reduced.

The boiling point of the (L) low-boiling solvent under atmospheric pressure is not particularly limited as long as it is less than 180 ℃, and is preferably 100 ℃ or more and less than 180 ℃.

Specific examples of the low boiling point solvent (L) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol N-propyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-N-propyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, tetrahydrofuran, methyl ethyl ketone, 2-heptanone, 3-heptanone, ethyl acetate, N-propyl acetate, isopropyl acetate, N-butyl acetate, isobutyl acetate, N-pentyl formate, isoamyl acetate, N-butyl propionate, ethyl butyrate, N-propyl butyrate, isopropyl butyrate, N-butyl butyrate, methyl pyruvate, ethyl pyruvate, N-propyl pyruvate, N, N-dimethylformamide, N, N-dimethylacetamide, N, N ', N' -tetramethylurea, propylene glycol monomethyl ether acetate, Dipropylene glycol dimethyl ether, cyclohexanone, 3-methoxybutanol, 3-methoxybutyl acetate, cyclohexyl acetate and cyclopentanone.

From the viewpoint of odor, the (S) solvent preferably does not contain alicyclic solvents such as cyclohexanone and cyclohexyl acetate, chain aliphatic ketone solvents having 6 or more carbon atoms such as 2-heptanone and 3-heptanone, and solvents such as anisole.

Among the low boiling point solvents (L), propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and 3-methoxybutanol are preferable because the components to be blended are well dissolved in the photosensitive resin composition and the photosensitive resin composition having good coatability can be easily prepared. The (S) solvent may contain 2 or more of these (L) low boiling point solvents in combination.

The combination of the (L) low boiling point solvent is preferably a combination of propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate, in terms of being able to dissolve the components of the photosensitive resin composition well and easily obtaining a photosensitive resin composition having a moderate drying property.

From the viewpoint of high-speed coating, the viscosity of the (L) low-boiling solvent is preferably less than 2cP (2mPa · s).

((H) high boiling point solvent)

(H) The high boiling point solvent is an organic solvent having a boiling point of 180 ℃ or higher and 300 ℃ or lower under atmospheric pressure. (H) The high-boiling solvent contains a compound having an aromatic hydrocarbon ring and an ester bond.

The boiling point of the (H) high-boiling point solvent under atmospheric pressure is preferably 180 ℃ or more and 250 ℃ or less, more preferably 180 ℃ or more and 220 ℃ or less, from the viewpoint of easily reducing the amount of the (H) high-boiling point solvent remaining in the coating film or the cured film.

By allowing (H) the high boiling point solvent to contain a compound having a boiling point within the above range and having the above specific structure, effects of suppressing precipitation of a resin having a Cardo structure and forming a smooth cured film can be simultaneously achieved.

By including (H) a high boiling point organic solvent having a boiling point of 180 ℃ or higher and 300 ℃ or lower in the photosensitive resin composition, rapid drying and bumping of the solvent can be suppressed when a coating film formed of the photosensitive resin composition is dried. This facilitates formation of a smooth coating film, and as a result, a smooth cured film is easily formed.

In addition, the photosensitive resin composition includes a resin having a Cardo structure as (a) the alkali-soluble resin. However, depending on the type of the (S) solvent, the resin having a Cardo structure may be difficult to dissolve. Therefore, in the conventional photosensitive resin composition, a resin having a Cardo structure is often precipitated.

However, in the case where the photosensitive resin composition contains a compound having an aromatic hydrocarbon group and an ester bond, the resin having a Cardo structure can be stably dissolved in the (S) solvent.

Further, some solvents among the (S) solvents used in the photosensitive resin composition have problems in terms of odor, such as the above-mentioned alicyclic solvents such as cyclohexanone and cyclohexyl acetate, chain aliphatic ketone solvents having 6 or more carbon atoms such as 2-heptanone and 3-heptanone, and solvents such as anisole.

On the other hand, compounds having an aromatic hydrocarbon ring and an ester bond do not generate an unpleasant odor. Therefore, a compound having an aromatic hydrocarbon ring and an ester bond is a preferable (S) solvent also in terms of odor.

(H) The high boiling point solvent may be a compound that can exist uniformly with the low boiling point solvent (L) in the photosensitive resin composition. Therefore, the (H) high boiling point solvent may be a solid under the temperature conditions at which the photosensitive resin composition is used.

Among the compounds having an aromatic hydrocarbon ring and an ester bond, which are used as the high boiling point solvent (H), 1 or more selected from the group consisting of benzyl esters of aliphatic carboxylic acids and alkyl esters of benzoic acids are preferable in terms of ease of dissolving the resin having a Cardo structure and low boiling point.

The number of carbon atoms of the benzyl ester of an aliphatic carboxylic acid and the alkyl ester of benzoic acid is not limited as long as the boiling point of these compounds under atmospheric pressure is in the range of 180 ℃ to 300 ℃.

Preferred specific examples of the compound having an aromatic hydrocarbon ring and an ester bond include alkyl esters of benzoic acid such as methyl benzoate (about 200 ℃ C.), ethyl benzoate (about 212 ℃ C.), n-propyl benzoate (about 230 ℃ C.) and n-butyl benzoate (about 250 ℃ C.); alkoxyalkyl esters of benzoic acid such as 2-hydroxyethyl benzoate (about 289 ℃), 2-methoxyethyl benzoate (about 225 ℃) and 2-ethoxyethyl benzoate (about 244 ℃); naphthoates such as methyl 2-naphthoate (about 290 ℃); aryl acetates such as phenyl acetate (about 195 deg.C), p-tolyl acetate (about 210 deg.C), m-tolyl acetate (about 210 deg.C), o-tolyl acetate (about 208 deg.C), p-methoxyphenyl acetate (about 246 deg.C), m-methoxyphenyl acetate (about 250 deg.C) and o-methoxyphenyl acetate (about 240 deg.C); aryl propionates such as phenyl propionate (about 211 ℃ C.) and p-tolyl propionate (about 232 ℃ C.); phenyl acetates such as methyl phenyl acetate (about 216 ℃ C.), ethyl phenyl acetate (about 226 ℃ C.) and n-propyl phenyl acetate (about 244 ℃ C.); 3-phenylpropionic acid esters such as methyl 3-phenylpropionate (about 238 ℃ C.) and ethyl 3-phenylpropionate (about 248 ℃ C.); phenoxyacetic acid esters such as phenoxyacetic acid methyl ester (about 244 ℃ C.) and phenoxyacetic acid ethyl ester (about 248 ℃ C.); benzyl esters of aliphatic carboxylic acids such as benzyl acetate (about 212 ℃), benzyl propionate (about 222 ℃), benzyl butyrate (about 240 ℃) and benzyl valerate (about 260 ℃); phenethyl esters of aliphatic carboxylic acids such as phenethyl acetate (about 238 ℃ C.), phenethyl propionate (about 244 ℃ C.), phenethyl butyrate (about 270 ℃ C.) and phenethyl valerate (about 288 ℃ C.); alkyl esters of substituted benzoic acids such as methyl parahydroxybenzoate (about 280 ℃), ethyl parahydroxybenzoate (about 238 ℃), methyl paramethoxybenzoate (about 244 ℃) and methyl anthranilate (about 248 ℃); alkyl esters of cinnamic acid such as methyl cinnamate (about 262 ℃ C.) and ethyl cinnamate (about 271 ℃ C.); dialkyl esters of benzenedicarboxylic acids such as dimethyl phthalate (about 283 ℃) and dimethyl terephthalate (about 288 ℃); and alkanoates of alkylene glycol monophenyl ethers such as ethylene glycol monophenyl ether acetate (about 231 ℃ C.) and ethylene glycol monophenyl ether propionate (about 262 ℃ C.).

The numerical value in parentheses immediately after the name of each solvent is the boiling point under atmospheric pressure.

The high boiling point solvent (H) may be used in combination of 2 or more.

(H) The high-boiling point solvent may contain a solvent other than the compound having an aromatic hydrocarbon ring and an ester bond. Specific examples of the solvent include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, n-methyl-2-pyrrolidone, 1, 4-butanediol diacetate, diethylene glycol mono-N-butyl ether acetate, 1, 6-hexanediol diacetate, epsilon-caprolactone, 1, 3-butanediol diacetate, diethylene glycol mono-ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol methyl-N-butyl ether, gamma-butyrolactone, dipropylene glycol methyl-N-propyl ether, and propylene glycol diacetate.

From the viewpoint of high-speed coating, the viscosity of the (H) high-boiling solvent is preferably less than 3cp (3mPa · s), and more preferably less than 2cp (2mPa · s).

(H) The content of the compound having an aromatic hydrocarbon ring and an ester bond in the high-boiling point solvent is not particularly limited within a range not interfering with the object of the present invention. Typically, the content of the compound having an aromatic hydrocarbon ring and an ester bond is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass, based on the mass of the (H) high-boiling point solvent.

The content of the (H) high-boiling solvent in the (S) solvent is 1 mass% or more and 30 mass% or less, preferably 5 mass% or more and 15 mass% or less. By using the high boiling point solvent in an amount within this range, not only can the desired effect obtained by using the (H) high boiling point solvent be obtained, but also the (H) high boiling point solvent is less likely to remain in the coating film or the cured film, and a cured film excellent in mechanical properties and the like is easily formed.

The (S) solvent may contain a solvent having a boiling point higher than 300 ℃ under atmospheric pressure within a range not interfering with the object of the present invention, but preferably consists of only (L) a low boiling point solvent and (H) a high boiling point solvent.

The content of the (S) solvent is preferably an amount to make the solid content concentration of the photosensitive resin composition 1 to 50 mass%, more preferably an amount to make it 5 to 35 mass%, particularly preferably an amount to make it 10 to 30 mass%, and particularly preferably an amount to make the solid content concentration of the photosensitive resin composition 10 to 20 mass% from the viewpoint of high-speed coating.

< other ingredients >

The photosensitive resin composition may contain various additives as needed. Examples of the additives include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an anti-agglomerating agent, a thermal polymerization inhibitor, a defoaming agent, and a surfactant.

Method for Forming cured film

The method for forming a cured film includes the steps of:

a step of forming a coating film by coating the photosensitive resin composition on a substrate; and

and exposing the coating film.

First, a photosensitive resin composition is applied onto a substrate using a contact transfer type coating apparatus such as a roll coater, a reverse coater, or a bar coater, a spin coater (rotary coating apparatus), a non-rotary (non-rotary) type coating apparatus, a slit coater, or a curtain coater, and a solvent is removed by heat drying or vacuum/reduced pressure drying as necessary to form a coating film. The material of the substrate is not particularly limited.

When high-speed coating is performed, a non-contact type coating apparatus is preferably used. For example, even when the Gantry Speed (GSP) of a non-contact non-rotating type coating apparatus is set to be in the range of, for example, 350mm/s to 400mm/s, a favorable coating film can be formed by the photosensitive resin composition of the present invention.

Next, the coating film is irradiated with an active energy ray such as an ultraviolet ray or an excimer laser to cure the coating film. When the cured film to be formed is a patterned material such as a black column spacer or a black matrix, the exposure to the coating film can be performed selectively in a position only at a portion to be cured.

The position-selective exposure is usually performed using a negative mask.

Exposure methodThe ultraviolet-emitting light source may be a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, or the like. The exposure amount varies depending on the composition of the photosensitive resin composition, but is preferably, for example, 10 to 600mJ/cm²Left and right.

When the substrate is a substrate in which an element is formed on a substrate, such as a TFT substrate, it is sometimes necessary to form a black columnar spacer or the like on the element or at a portion of the substrate paired with the substrate on which the element is formed, the portion facing the element. In this case, it is necessary to change the height of the black columnar spacer at the portion where the element is formed and other portions in consideration of the height of the element. Therefore, in such a case, it is preferable to perform exposure through a halftone mask.

The method for forming a black columnar spacer according to the present invention includes the steps of:

a coating step of coating the photosensitive resin composition on a substrate to form a photosensitive resin layer;

an exposure step of exposing the photosensitive resin layer according to a predetermined pattern of the black columnar spacer; and

and a developing step of developing the exposed photosensitive resin layer to form a pattern of black columnar spacers.

First, in the coating step, the photosensitive resin composition of the present invention is coated on a substrate on which a black columnar spacer is to be formed using a contact transfer type coating apparatus such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating apparatus such as a spin coater (a rotary coating apparatus), a non-rotary type coating apparatus, a slit coater, or a curtain coater, and the solvent is removed by heat drying or vacuum/reduced pressure drying as necessary to form a photosensitive resin layer.

When high-speed coating is performed, a non-contact type coating apparatus is preferably used. For example, even when the Gantry Speed (GSP) of a non-contact non-rotating type coating apparatus is set to be in the range of, for example, 350mm/s to 400mm/s, a favorable coating film can be formed by the photosensitive resin composition of the present invention.

Next, in the exposure step, the photosensitive resin layer is irradiated with an active energy ray such as ultraviolet light or an excimer laser through a negative mask, and the photosensitive resin layer is partially exposed according to the pattern of the black columnar spacer. In the exposure, a light source emitting ultraviolet rays such as a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. The exposure amount varies depending on the composition of the photosensitive resin composition, but is preferably, for example, 10 to 600mJ/cm²Left and right.

When the substrate is a substrate in which an element is formed on a substrate, such as a TFT substrate, it is sometimes necessary to form a black columnar spacer on the element or at a portion of the substrate paired with the substrate on which the element is formed, the portion facing the element. In this case, it is necessary to change the height of the black columnar spacer at the portion where the element is formed and other portions in consideration of the height of the element. Therefore, in such a case, it is preferable to perform exposure through a halftone mask. By using the photosensitive resin composition according to the present invention, black columnar spacers having different heights can be easily formed by exposure through a halftone mask.

In the case where the exposure of the coating film is performed position-selectively, the exposed coating film is usually developed using a developer.

By developing the exposed coating film, a patterned cured film such as a black columnar spacer or a black matrix can be formed.

The developing method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developer include organic developers such as monoethanolamine, diethanolamine, and triethanolamine; aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salts, and the like.

The coating film subjected to exposure or exposure and development is subjected to post-baking and cured by heating. The post-baking is preferably carried out at 150 to 250 ℃ for 15 to 60 minutes.

When the photosensitive resin composition contains pigment particles, it may be difficult to form a smooth cured film due to the influence of pigment particles and pigment particle aggregates, but when the above-described photosensitive resin composition is used to form a cured film by the above-described method, a smooth cured film having a surface roughness Ra of 15nm or less (preferably less than 10nm) can be formed even when the photosensitive resin composition contains pigment particles.

Examples

[ preparation example 1]

The procedure for synthesizing the Cardo resin (A-1) is as follows.

First, a 500ml four-necked flask was charged with 235g of bisphenol fluorene type epoxy resin (epoxy equivalent: 235), 110mg of tetramethylammonium chloride, 100mg of 2, 6-di-t-butyl-4-methylphenol and 72.0g of acrylic acid, and heated and dissolved at 90 to 100 ℃ while blowing air at a rate of 25 ml/min. Subsequently, the temperature of the solution was gradually increased while the solution was cloudy, and the solution was heated to 120 ℃ to be completely dissolved. At this time, the solution gradually became transparent and viscous, and stirring was continued in this state. During this time, the acid number was determined and stirring with heating was continued until the acid number was below 1.0mg KOH/g. The acid value required 12 hours to reach the target value. Then, the mixture was cooled to room temperature to obtain a bisphenol fluorene type epoxy acrylate represented by the following formula (a-4) which was colorless and transparent and was solid.

Then, 307.0g of the bisphenol fluorene type epoxy acrylate obtained in the above manner was dissolved by adding 600g of 3-methoxybutyl acetate, and then 80.5g of benzophenone tetracarboxylic dianhydride and 1g of tetraethylammonium bromide were mixed, and the mixture was reacted at 110 to 115 ℃ for 4 hours while gradually raising the temperature. After confirming the disappearance of the acid anhydride group, 38.0g of 1,2,3, 6-tetrahydrophthalic anhydride was mixed and reacted at 90 ℃ for 6 hours to obtain a Cardo resin (a-1). The disappearance of the acid anhydride group was confirmed by IR spectroscopy.

The Cardo resin (a-1) is a resin represented by the above formula (a-1).

Example 1, example 2 and comparative examples 1 to 12

The photosensitive resin compositions of examples and comparative examples were obtained by dissolving 25 parts by mass of the Cardo resin (a-1) obtained in preparation example 1, 10 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 3- (2-methylbenzoyl) -6- [1- (acetoxyimino) ethyl ] -9-ethyl-9H-carbazole as a photopolymerizable compound, and a black pigment dispersion (60 parts by mass in terms of solid content) in a solvent so that the solid content concentration became 14 mass%.

The solvent composition was 45 mass% of 3-Methoxybutyl Acetate (MA), 45 mass% of Propylene Glycol Monomethyl Ether Acetate (PGMEA), and 10 mass% of an additive solvent of the type described in table 1.

Resin deposition was evaluated for additive solvents of the types shown in table 1 in the following manner.

2 parts by mass of the Cardo resin (a-1) obtained in preparation example 1 was dissolved in 100 parts by mass of the solvent (alone) described in table 1, and left for 3 days to confirm the presence or absence of precipitation. The results of the cases where no deposition was observed are indicated by "o" and the cases where deposition was observed are indicated by "x", respectively, in table 1.

The obtained photosensitive resin composition was evaluated for smoothness of the cured film and pigment dispersion stability (change in viscosity and increase and decrease in foreign matter) by the following methods. The results of these evaluations are shown in Table 1.

[ method for evaluating smoothness of cured film ]

The obtained photosensitive resin composition was applied to a glass substrate (thickness: 0.7mm) of 680X 880mm using a non-rotating type coating apparatus TR45000 (manufactured by Tokyo Kogyo Co., Ltd.), and dried under reduced pressure of 65Pa from atmospheric pressure to form a coating film having a film thickness of 1.0. mu.m. Next, the coating film was irradiated with ultraviolet rays (exposure amount: 100 mJ/cm) using an ultraviolet ray irradiation apparatus (product name: MPA6000, manufactured by Canon corporation)²). The coating film after exposure was developed in a 0.04 mass% KOH aqueous solution at room temperature for 60 seconds, and then post-baked at 230 ℃ for 30 minutes, thereby obtaining a cured film.

The surface roughness of the obtained cured film was measured by a stylus type film thickness meter (NSPR1300, ULVAC). The measured surface roughness (ra (nm)) was used to evaluate the quality according to the following criteria. The results are shown in Table 1.

(smoothness evaluation criteria)

Very good: ra is 5nm to less than 10nm

O: ra is 10nm or more and 15nm or less

And (delta): ra is more than 15nm and less than 25nm

X: ra is more than 25nm

[ method for evaluating pigment dispersion stability (change in viscosity or increase or decrease in foreign matter) ]

The obtained photosensitive resin composition was left at 25 ℃ for 30 days, and then the change in viscosity and the change in the number of foreign substances were evaluated according to the following criteria. As for the change in the number of foreign matters, a coating film after drying under reduced pressure was formed in the same manner as the method for evaluating the smoothness of a cured film, and evaluation was performed using the formed coating film. The results are shown in Table 1.

(evaluation criterion of viscosity Change)

O: the photosensitive resin composition has no increase in viscosity before and after standing

X: the photosensitive resin composition has an increased viscosity before and after standing

(evaluation criteria for number of foreign matters change)

O: the coating film after drying under reduced pressure had no increase in foreign matter before and after standing

X: the coating film after drying under reduced pressure had increased foreign matter before and after standing

[ Table 1]

As is clear from examples 1 and 2, in the case where the photosensitive resin composition containing a resin having a Cardo structure contains a compound having an aromatic hydrocarbon ring and an ester bond and having a boiling point of 180 ℃ or higher under atmospheric pressure as the (S) solvent, precipitation of the resin is suppressed, a smooth cured film can be formed, and the dispersibility of the pigment is also good.

As is clear from comparative examples 1 to 12, when the added solvent is not a compound having an aromatic hydrocarbon ring and an ester bond, or the boiling point of the added solvent under atmospheric pressure is less than 180 ℃, the effects of suppressing precipitation of a resin having a Cardo structure and forming a smooth cured film cannot be simultaneously achieved.

[ example 3 and comparative examples 13 to 16 ]

Photosensitive resin compositions were prepared in the same manner as in example 1, except that the composition of the solvent was changed as shown in table 2.

[ Table 2]

The obtained photosensitive resin composition was coated on a glass substrate (thickness: 0.7mm) of 680mm × 880mm at a high speed using a non-spin coating apparatus TR45000 (manufactured by tokyo chemical industries), and then dried under reduced pressure of 65Pa from atmospheric pressure to obtain a photosensitive resin composition layer. The coatability by high-speed coating and the surface state of the obtained photosensitive resin composition layer were evaluated according to the following criteria. The results of these evaluations are shown in Table 2.

(coating speed evaluation criteria)

O: the speed of no liquid break or liquid return is above GSP 350mm/s

And (delta): the speed of no liquid break or liquid return is above 340mm/s and less than 350mm/s of GSP

X: the speed of no liquid break or liquid return is below GSP 330mm/s

(surface evaluation criteria)

O: no abnormality or foreign matter due to bumping caused by VCD (vacuum drying) was observed

X: abnormalities and foreign matters due to bumping caused by VCD (vacuum drying) were observed

Claims (10)

1. A photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (S) a solvent,

the alkali-soluble resin (A) contains a resin having a Cardo structure,

the (S) solvent comprises (L) a low-boiling solvent having a boiling point of less than 180 ℃ under atmospheric pressure and (H) a high-boiling solvent having a boiling point of 180 ℃ or higher and 250 ℃ or lower under atmospheric pressure,

the (H) high-boiling solvent contains a compound having an aromatic hydrocarbon ring and an ester bond,

the content of the (H) high-boiling solvent in the (S) solvent is 1 to 30 mass% inclusive,

the resin having a Cardo structure is a resin represented by the following formula (a-1),

in the above formula (a-1), X^aRepresents a group represented by the following formula (a-2), Y^aZ represents a residue obtained by removing an acid anhydride group, i.e., -CO-O-CO-, from a dicarboxylic acid anhydride^aRepresents a residue obtained by removing 2 acid anhydride groups from tetracarboxylic dianhydride, m represents an integer of 0 to 20,

in the above formula (a-2), R^a1Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms or a halogen atom, R^a2Each independently represents a hydrogen atom or a methyl group, W^aRepresents a single bond or a group represented by the following formula (a-3),

2. the photosensitive resin composition according to claim 1, wherein the boiling point of the high boiling point solvent (H) is 180 ℃ or higher and 220 ℃ or lower at atmospheric pressure.

3. The photosensitive resin composition according to claim 1 or 2, wherein the compound having an aromatic hydrocarbon ring and an ester bond is at least 1 compound selected from the group consisting of benzyl esters of aliphatic carboxylic acids and alkyl esters of benzoic acids.

4. The photosensitive resin composition according to claim 1 or 2, wherein the content of the (H) high-boiling solvent in the (S) solvent is 5% by mass or more and 15% by mass or less.

5. The photosensitive resin composition according to claim 1 or 2, which comprises (D) a pigment.

6. A cured film formed from a cured product of the photosensitive resin composition according to any one of claims 1 to 4.

7. A cured film formed from a cured product of the photosensitive resin composition according to claim 5.

8. The cured film according to claim 6 or 7, wherein the cured film has a surface roughness Ra of 15nm or less.

9. A method for forming a cured film, comprising the steps of:

a step of forming a coating film by coating the photosensitive resin composition according to any one of claims 1 to 5 on a substrate; and

and exposing the coating film.

10. The method of forming a cured film according to claim 9, the method comprising: the exposure of the coating film is performed in a position-selective manner, and further, the exposed coating film is developed.