CN105372938B

CN105372938B - Photosensitive resin composition and carbon black

Info

Publication number: CN105372938B
Application number: CN201510505614.XA
Authority: CN
Inventors: 石川达郎; 山口尚人; 黑子麻祐美; 盐田大
Original assignee: Tokyo Ohka Kogyo Co Ltd
Current assignee: Tokyo Ohka Kogyo Co Ltd
Priority date: 2014-08-19
Filing date: 2015-08-17
Publication date: 2020-06-23
Anticipated expiration: 2035-08-17
Also published as: JP6401545B2; KR101803146B1; JP2016045220A; KR20160022264A; TW201610588A; CN105372938A; TWI667545B

Abstract

The invention provides a photosensitive resin composition capable of forming a black pattern which has excellent adhesion and insulation to a substrate and is not easy to reduce the insulation caused by heating, a method for forming a patterned cured product using the photosensitive resin composition, a patterned cured product formed by using the photosensitive resin composition, a display device provided with a black matrix or a black column spacer formed by using the photosensitive resin composition, and carbon black mixed in the photosensitive resin composition. The light-blocking agent (D) is a photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C) and a light-blocking agent (D), and the light-blocking agent (D) is a mixture of a light-blocking agent (D) and carbon black treated with a silane coupling agent having a specific structure.

Description

Photosensitive resin composition and carbon black

Technical Field

The present invention relates to a photosensitive resin composition comprising (a) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a light-shading agent, a method for forming a patterned cured product using the photosensitive resin composition, a patterned cured product formed using the photosensitive resin composition, a display device provided with a black matrix (ブラックマトリクス) or a black columnar spacer (ブラックカラムスペーサ) formed using the photosensitive resin composition, and carbon black suitably used as the light-shading agent component (D) in the photosensitive resin composition.

Background

When a panel for a display device such as a liquid crystal display device is formed, various patterns having various functions are formed on a substrate for the panel. Examples of such a pattern include a black matrix pattern provided for blocking light between pixels, and a black columnar spacer pattern formed to keep a constant gap (cell gap) between two substrates.

As a method for forming a pattern of the black matrix or black columnar spacer, a method for forming a pattern by photolithography using a photosensitive resin composition containing carbon black as a light-shielding agent has been proposed in order to facilitate formation of a pattern having excellent dimensional accuracy and positional accuracy (see patent documents 1 and 2).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2000-199967

Patent document 2: japanese patent laid-open publication No. 2011-

Disclosure of Invention

Problems to be solved by the invention

However, the methods described in patent documents 1 and 2 have the following problems: depending on the type of carbon black, a fine pattern having excellent adhesion to a substrate is not easily formed, a pattern having excellent insulation properties is not easily formed, or the insulation properties of the formed pattern are easily lowered by heating.

The present invention has been made in view of the above problems, and an object thereof is to provide a photosensitive resin composition capable of forming a black pattern which is excellent in adhesion to a substrate and insulation properties and hardly causes a decrease in insulation properties due to heating, a method for forming a patterned cured product using the photosensitive resin composition, a display device including a black matrix or a black columnar spacer formed using the photosensitive resin composition, and carbon black blended in the photosensitive resin composition.

Means for solving the problems

The present inventors have found that the above problems can be solved by adding a light-shielding agent (D) comprising carbon black treated with a silane coupling agent having a specific structure to a photosensitive resin composition comprising (a) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a light-shielding agent, and have completed the present invention.

The first embodiment of the present invention is a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a light-shielding agent,

(D) the light-shading agent is a photosensitive resin composition containing carbon black treated by a silane coupling agent represented by the following formula (1).

R¹ _pR² _(3-p)Si-R³-NH-C(O)-Y-R⁴-X…(1)

(in the formula (1), R¹Is alkoxy, R²Is alkyl, p is an integer of 1 to 3, R³Is alkylene, Y is-NH-, -O-or-S-, R⁴Is a single bond or alkylene, X is a monocyclic or polycyclic nitrogen-containing heteroaryl group which may have a substituent, and-Y-R in X⁴-the bonded ring is a nitrogen-containing six-membered aromatic ring, -Y-R⁴-to a carbon atom of the above nitrogen-containing six-membered aromatic ring. )

A second aspect of the present invention is a method for forming a patterned cured product, including:

a step of forming a coating film by coating the photosensitive resin composition according to the first aspect on a substrate;

a step of exposing the coating film with position selectivity; and

and developing the exposed coating film.

A third aspect of the present invention is a patterned cured product formed using the photosensitive resin composition according to the first aspect.

A fourth aspect of the present invention is a display device including a black matrix or a black columnar spacer formed using the photosensitive resin composition according to the first aspect.

A fifth aspect of the present invention is carbon black treated with a silane coupling agent represented by formula (1).

R¹ _pR² _(3-p)Si-R³-NH-C(O)-Y-R⁴-X…(1)

Effects of the invention

According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a black pattern which is excellent in adhesion to a substrate and insulation properties and in which insulation properties are not easily lowered by heating, a method for forming a patterned cured product using the photosensitive resin composition, a patterned cured product formed using the photosensitive resin composition, a display device provided with a black matrix or a black columnar spacer formed using the photosensitive resin composition, and carbon black blended in the photosensitive resin composition.

Detailed Description

Photosensitive resin composition

The photosensitive resin composition comprises (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a light-shielding agent. (D) The light-shading agent includes carbon black treated with a silane coupling agent having a predetermined structure described later. Hereinafter, essential or optional components contained in the photosensitive resin composition will be described.

Alkali soluble resin (A)

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

(A) The alkali-soluble resin is not particularly limited as long as it exhibits the alkali-solubility, and can be appropriately selected from conventionally known resins. Examples of a resin suitable as the alkali-soluble resin (A) include resins having a Cardo structure (カルド structure) (A1).

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.

[ solution 1]

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

[ solution 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).

[ solution 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 dicarboxylic anhydrides include: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylene (エンドメチレン) tetrahydrophthalic anhydride, chlorendic anhydride, methyl tetrahydrophthalic anhydride, glutaric anhydride, and the like.

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

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

(A1) The mass average molecular weight (Mw: measured by Gel Permeation Chromatography (GPC) in terms of polystyrene) of the resin having a Cardo structure is preferably 1000 to 40000, and more preferably 2000 to 30000. By setting the above range, good developability can be obtained, and sufficient heat resistance and film strength can be obtained.

In addition, from the viewpoint of easy formation of a cured product having excellent breaking strength and adhesion to a substrate, (a2) a copolymer in which at least (a1) an unsaturated carboxylic acid is polymerized can also 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 the like. Among them, (meth) acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, ease of handling, and the like. These (a1) unsaturated carboxylic acids may be used singly 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 unsaturated compound having an alicyclic epoxy group. The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include: cyclopentyl, cyclohexyl, and the like. Further, as polycyclic alicyclic groups, there may be mentioned: norbornyl, isobornyl, tricyclic nonyl, tricyclic decyl, tetracyclododecyl and the like. These alicyclic epoxy group-containing unsaturated compounds (a2) may be used singly 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 2-16). Among them, in order to achieve a suitable developability, compounds represented by the following formulae (a2-1) to (a2-6) are preferable, and compounds represented by the following formulae (a2-1) to (a2-4) are more preferable.

[ solution 4]

[ solution 5]

[ solution 6]

In the above formula, R¹¹Represents a hydrogen atom or a methyl group, R¹²Represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R¹³Represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10. As R¹²Preferred examples of the alkylene group include linear or branched alkylene groups such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene and hexamethylene. As R¹³For example, methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH₂-Ph-CH₂- (Ph represents phenylene).

(A2) In the copolymer, (a3) an alicyclic group-containing unsaturated compound having no epoxy group may be copolymerized together with the (a1) unsaturated carboxylic acid and (a2) the alicyclic epoxy group-containing unsaturated compound.

The alicyclic group-containing unsaturated compound (a3) is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include: cyclopentyl, cyclohexyl, and the like. Further, as polycyclic alicyclic groups, there may be mentioned: adamantyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl and the like. These alicyclic group-containing unsaturated compounds (a3) may be used singly 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 achieve a suitable developability, compounds represented by the following formulae (a3-3) to (a3-8) are preferable, and compounds represented by the following formulae (a3-3) and (a3-4) are more preferable.

[ solution 7]

[ solution 8]

In the above formula, R²¹Represents a hydrogen atom or a methyl group, R²²Represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R²³Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As R²²The alkylene group is preferably a single bond, a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group. As R²³Preferably, for example, methyl and ethyl.

In addition, in the copolymer (a2), the unsaturated compound (a4) containing an epoxy group, which does not have an alicyclic group, may be copolymerized together with the unsaturated carboxylic acid (a1), the unsaturated compound (a2) containing an alicyclic epoxy group, and the unsaturated compound (a3) containing an alicyclic group.

Examples of the epoxy group-containing unsaturated compound (a4) include epoxy alkyl (meth) acrylates such as glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, and 6, 7-epoxyheptyl (meth) acrylate, epoxy alkyl (meth) acrylates such as α -glycidyl ethacrylate, α -n-glycidyl n-propylacrylate, α -n-butyl glycidyl acrylate, and epoxy alkyl (α) -alkylacrylates such as 6, 7-epoxyheptyl (meth) acrylate, α -ethylacrylate, and the like, and 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, and these epoxy group-containing unsaturated compounds (a4) may be used alone or in combination of 2 or more.

In addition, in the copolymer (a2), other compounds than the above-mentioned ones may be further copolymerized. 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) acrylates 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 the like.

Examples of the (meth) acrylamides 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 the like.

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, and tetrahydrofurfuryl vinyl ether; 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 the like.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl diethylacetate, vinyl valerate, vinyl caproate, 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 styrenes 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 the like.

The proportion of the constituent 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.

When the copolymer (a2) contains the constituent unit derived from the alicyclic epoxy group-containing unsaturated compound (a2) and the constituent unit derived from the epoxy group-containing unsaturated compound (a4), the total of the proportion of the constituent unit derived from the alicyclic epoxy group-containing unsaturated compound (a2) in the copolymer (a2) and the proportion of the constituent 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 constituent 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 setting the proportion of the constituent 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 improved.

When the copolymer (a2) contains a constituent unit derived from the alicyclic group-containing unsaturated compound (A3), the proportion of the constituent 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 mass average molecular weight of the copolymer is preferably 2000 to 200000, and more preferably 3000 to 30000. By setting the above range, the photosensitive resin composition tends to have a balanced film forming ability and developability after exposure.

Further, as the (a) alkali-soluble resin, a resin containing a copolymer (A3) having at least a constituent unit derived from the above (a1) unsaturated carboxylic acid and a constituent unit having a site polymerizable with the later-described (B) photopolymerizable monomer, or a copolymer (A4) having at least a constituent unit derived from the above (a1) unsaturated carboxylic acid, a constituent unit derived from the above (a2) alicyclic epoxy group-containing unsaturated compound and/or (A4) epoxy group-containing unsaturated compound, and a constituent unit having a site polymerizable with the later-described photopolymerizable monomer (B) may also be preferably used. (A) When the alkali-soluble resin contains the copolymer (A3) or the copolymer (a4), the adhesion of the photosensitive resin composition to the substrate and the breaking strength of the photosensitive resin composition after curing can be improved.

(A3) The copolymer and the (a4) copolymer may be: further, the copolymer (A2) may be copolymerized with other compounds such as (meth) acrylates, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, etc.

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

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

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

(A4) The proportion of the constituent unit having a site capable of polymerizing with the photopolymerizable monomer (B) in the copolymer is preferably 1 to 45% by mass, and more preferably 5 to 40% by mass. (A4) When the copolymer contains the respective constituent units in such a ratio, a photosensitive resin composition capable of forming black columnar spacers excellent in adhesion to a substrate can be easily obtained.

(A3) The mass average molecular weight of the copolymer (A4) and the copolymer (B) is preferably 2000 to 50000, more preferably 5000 to 30000. By setting the above range, the photosensitive resin composition tends to have a balanced film forming ability and developability after exposure.

(A) The content of the alkali-soluble resin is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, based on the solid content of the photosensitive resin composition. When the alkali-soluble resin (a) is used in an amount within the above range, a photosensitive resin composition having excellent developability can be easily obtained.

< (B) photopolymerizable monomer

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

Examples of monofunctional monomers include: (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, methyl (meth) acrylate, N-hydroxymethyl (meth) acrylamide, N-hydroxymethacrylamide, N-methylol (meth) acrylamide, N-acrylic acid, N-ethylmethacrylic (meth) acrylate, N-ethylhexylacrylic acid, 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, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3, 3-tetrafluoropropyl (meth) acrylate, half-esters of phthalic acid derivatives, and the like. These monofunctional monomers may be used alone or in combination of 2 or more.

On the other hand, examples of the polyfunctional monomer include: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol 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, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, propylene glycol di (meth) acrylate, propylene, 2, 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), trimethylhexamethylene diisocyanate and the reaction product of hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, acrylic acid glycidyl methacrylate, acrylic acid, and methacrylic acid, Polyfunctional monomers such as (meth) acrylamide methylene ether and condensates of polyhydric alcohols and N-methylol (meth) acrylamide, and 1,3, 5-triacryloylhexahydro-1, 3, 5-triazine. These polyfunctional monomers may be used alone or in combination of 2 or more.

(B) The content of the photopolymerizable monomer is preferably 3 to 30% by mass, more preferably 5 to 20% by mass, based on the solid content of the photosensitive resin composition. By setting the range, a balance among 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-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, bis (4-dimethylaminophenyl) ketone, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, 4-benzoyl-4' -methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentylbenzoate, benzoyl- β -methoxyethylethylacetal, benzildimethylketal, 1-phenyl-1, 2-propanedione-2- (ethoxycarbonyl) triazine, 2-p-bromobenzoin-butyl) benzophenone, 2-propyl-1-phenyl-1-one, 2-hydroxy-2-methyl-1-propane-1-one, 1-hydroxy-2-methyl-1-propane-1-one, 1-2-propane-1-one, 1-hydroxy-2-methyl-1-propane-1-one, 1-2-propyl-1-one, 1-2-1-2-one, 1-2-propyl-1-one, 1-2-1-one, 1-2-one, 1-2-4-isopropyl benzophenone, 1-2-4-1-isopropyl benzophenone, 1-2-1-4-1-one, 1-4-2-1-2-isopropyl benzophenone, 1-2-4-2-one, 1-4-2-1-4-2-isopropyl benzophenone, 1-one, 1-2-4-2-one, 1-2-4-1-methyl-isopropyl phenyl-4-2-4-methyl-2-1-4-1-2-methyl-2-1-2-1-2-isopropyl benzophenone, 1-2-methyl-2-1-2-methyl-1-2-methyl-4-2-methyl-isopropyl phenyl-methyl-4-methyl-isopropyl benzophenone, 1-methyl-phenyl-methyl-phenyl-one, 1-methyl-phenyl-methyl-phenyl-one, 1-phenyl-methyl-one, 1-phenyl-one, 1-phenyl-one, 1-phenyl.

The photosensitive resin composition preferably contains an oxime ester compound as the photopolymerization initiator (C) in the above-described compounds. The oxime ester compound is a compound in which two organic groups are bonded to each other via an oxime ester bond represented by ═ N-O-CO-. When an oxime ester compound is added to the photosensitive resin composition as (C) the photopolymerization initiator, a photosensitive resin composition having excellent exposure sensitivity can be easily obtained.

The oxime ester compound used as (C) the photopolymerization initiator is not particularly limited. As the photopolymerization initiator (C), a conventionally known oxime ester compound can be used. Among the oxime ester compounds, a compound represented by the following formula (c1) is preferable.

[ solution 9]

In the above formula (c1), R^c1Represents an alkyl group having 1 to 10 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. a is 0 or 1. R^c2Represents an alkyl group having 1 to 10 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. R^c3Represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have a substituent.

R^c1In the case of an alkyl group having 1 to 10 carbon atoms which may have a substituent, the kind of the substituent contained in the alkyl group is not particularly limited within the range not to impair the object of the present invention.

Examples of suitable substituents that an alkyl group having 1 to 10 carbon atoms may have include: 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, a naphthoyloxy group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a phenyloxy group which may have a, A heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group, and the like.

The alkyl group having 1 to 10 carbon atoms may be linear or branched. In this case, the number of carbon atoms in the alkyl group is preferably 1 to 8, more preferably 1 to 5.

R^c1In the case of a phenyl group which may have a substituent, the kind of the substituent is not particularly limited within a range not to impair the object of the present invention. Suitable examples of the substituent that the phenyl group may have include: an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a 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, naphthyl which may have a substituent, naphthoxy which may have a substituent, naphthoyl which may have a substituent, naphthoxycarbonyl which may have a substituent, naphthoyloxy which may have a substituent, naphthylalkyl which may have a substituent, heterocyclic group which may have a substituent, amino group substituted with 1 or 2 organic groups, morpholin-1-yl and piperazin-1-yl, halogen, nitro, cyano and the like. R^c1When the phenyl group is a phenyl group which may have a substituent and the phenyl group has a plurality of substituents, the plurality of substituents may be the same or different.

When the substituent of the phenyl group is an alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, particularly preferably 1 to 3, and most preferably 1. The alkyl group may be linear or branched. Specific examples of the case where the substituent group of the phenyl group is an 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, and the like. In addition, the alkyl group may contain an ether bond (-O-) in the carbon chain. In this case, examples of the substituent of the phenyl group include an alkoxyalkyl group and an alkoxyalkoxyalkyl group. When the substituent of the phenyl group is an alkoxyalkyl group, the substituent is preferably-R^c4-O-R^c5The group shown. R^c4Is a linear or branched alkylene group having 1 to 10 carbon atoms. R^c5Is a linear or branched alkyl group having 1 to 10 carbon atoms. R^c4The number of carbon atoms of (A) is preferably 1 to 8, more preferably 1 to 5, and particularly preferably 1 to 3. R^c5The number of carbon atoms of (A) is preferably 1 to 8, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. Examples of the alkyl group having an ether bond in the carbon chain include: methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, and methoxypropyl, and the like.

When the substituent of the phenyl group is an alkoxy group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 6. The alkoxy group may be linear or branched. Specific examples of the substituent group of the phenyl group being an alkoxy group include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, sec-pentoxy, tert-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, isooctoxy, sec-octoxy, tert-octoxy, n-nonoxy, isononyloxy, n-decyloxy, and isodecyloxy, and the like. In addition, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include: methoxyethoxy, ethoxyethoxy, 2-methoxy-1-methylethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propoxyethoxyethoxy, methoxypropoxy and the like.

When the substituent of the phenyl group is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 to 10, more preferably 3 to 6. Specific examples of the case where the substituent group of the phenyl group is a cycloalkyl group include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, and the like. Specific examples of the case where the substituent group of the phenyl group is a cycloalkoxy group include: cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy, and the like.

When the substituent of the phenyl group is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 to 20, more preferably 2 to 7. Specific examples of the case where the substituent group of the phenyl group is a saturated aliphatic acyl group include: acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2-dimethylpropionyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, and n-hexadecanoyl, and the like. Specific examples of the case where the substituent group of the phenyl group is a saturated aliphatic acyloxy group include: acetoxy, propionyloxy, n-butyryloxy, 2-methylpropionyloxy, n-valeryloxy, 2-dimethylpropionyloxy, n-hexanoyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n-undecanoyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanoyloxy, and n-hexadecanoyloxy, and the like.

When the substituent of the phenyl group is alkoxycarbonyl, the number of carbon atoms is preferably 2 to 20, more preferably 2 to 7. Specific examples of the substituent group of the phenyl group being an alkoxycarbonyl group include: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl and the like.

When the substituent of the phenyl group is phenylalkyl, the number of carbon atoms is preferably 7 to 20, more preferably 7 to 10, when the substituent of the phenyl group is naphthylalkyl, the number of carbon atoms is preferably 11 to 20, more preferably 11 to 14, specific examples of the substituent of the phenyl group are benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl, and when the substituent of the phenyl group is naphthylalkyl, specific examples of the substituent of the phenyl group are α -naphthylmethyl, β -naphthylmethyl, 2- (α -naphthyl) ethyl and 2- (β -naphthyl) ethyl.

When the substituent of the phenyl group is a heterocyclic group, the heterocyclic group is a five-or six-membered monocyclic ring containing at least 1N, S, O atoms, or a heterocyclic group in which the monocyclic rings are condensed with each other or with a benzene ring. When the heterocyclic group is a condensed ring, the number of condensed rings is set to 3. 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, and the like. When the substituent of the phenyl group is a heterocyclic group, the heterocyclic group may further have a substituent.

When the substituent of the phenyl group is an amino group substituted with 1 or 2 organic groups, examples of suitable organic groups 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, a saturated aliphatic acyloxy group having 2 to 20 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, and a heterocyclic group.

Examples of the substituent in the case where the phenyl group, the naphthyl group and the heterocyclic group contained in the substituent of the phenyl group further have a substituent include: an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a 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. When the phenyl group, naphthyl group and heterocyclic group contained in the substituent group of the phenyl group further have a substituent group, the number of the substituent group is not limited within the range not hindering the object of the present invention, and is preferably 1 to 4. When the phenyl group, the naphthyl group and the heterocyclic group contained in the substituent group of the phenyl group have a plurality of substituents, the plurality of substituents may be the same or different.

R as defined above^c1Among the substituents in the case of a phenyl group which may have a substituent, an alkyl group or an alkoxyalkyl group is preferable.

R^c1In the case of a phenyl group which may have a substituent, the number of substituents and the bonding position of the substituents are not particularly limited within the range not to hinder the object of the present invention. R^c1In the case of a phenyl group which may have a substituent, the phenyl group which may have a substituent is preferably an o-tolyl group which may have a substituent, from the viewpoint of excellent generation efficiency of a base.

R^c1In the case of a carbazolyl group which may have a substituent(s), the substituent(s) is/areThe present invention is not particularly limited insofar as the object of the present invention is not hindered. Examples of suitable substituents that the carbazolyl group may have at a carbon atom include: an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a 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 phenylcarbonyl 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 having 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylcarbonyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, Optionally substituted naphthoyloxy, optionally substituted naphthylalkyl having 11 to 20 carbon atoms, optionally substituted heterocyclic group, optionally substituted heterocyclic carbonyl group, amino group substituted with 1 or 2 organic groups, morpholin-1-yl and piperazin-1-yl, halogen, nitro, cyano, and the like.

R^c1In the case of a carbazolyl group which may have a substituent, examples of suitable substituents which the carbazolyl group may have on the nitrogen atom include: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a 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, a heterocyclic carbonyl group which may have a substituent, and the like. Among these substituents, an alkane having 1 to 20 carbon atoms is preferableThe alkyl group is more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an ethyl group.

Specific examples of the substituent which may be contained in the carbazolyl group include alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acyloxy, phenylalkyl which may be substituted, naphthylalkyl which may be substituted, heterocyclic group which may be substituted, and amino substituted with 1 or 2 organic groups, and R^c1Examples of the substituent which the phenyl group has in the case of the phenyl group which may have a substituent are the same.

R^c1Among them, examples of the substituent in the case where the phenyl group, the naphthyl group and the heterocyclic group contained in the substituent of the carbazolyl group further have a substituent include: an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; benzoyl substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group and a phenyl group; a monoalkylamino group having an alkyl group 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, the naphthyl group and the heterocyclic group contained in the substituent group of the carbazolyl group further have a substituent group, the number of the substituent groups is not limited within a range not to impair the object of the present invention. In this case, the number of the substituents is preferably 1 to 4. When the phenyl group, the naphthyl group and the heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different.

R^c2The alkyl group may have a substituent(s) and has 1 to 10 carbon atoms, or a substituted phenyl group, or a substituted carbazolyl group.

R^c2When the alkyl group has 1 to 10 carbon atoms and may have a substituent, the alkyl group may be a straight chain or a branched chain. In this case, the number of carbon atoms in the alkyl group is preferably 1 to 8, more preferably 1 to 81～5。

R^c2In (3), the substituent group of the alkyl group or the phenyl group is not particularly limited as long as the object of the present invention is not hindered.

Examples of suitable substituents that an alkyl group may have on a carbon atom include: 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, a naphthoyloxy group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a phenyloxy group which may have a, A heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group, and the like.

Examples of suitable substituents that a phenyl group may have on a carbon atom include those exemplified above as alkyl groups that may have suitable substituents on a carbon atom, and alkyl groups having 1 to 20 carbon atoms.

Specific examples of the substituent which may be contained in the alkyl group or the phenyl 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^c1Examples of the substituent which the phenyl group has in the case of the phenyl group which may have a substituent are the same.

R^c2Among them, examples of the substituent in the case where the phenyl group, the naphthyl group and the heterocyclic group contained in the alkyl group or the substituent contained in the phenyl group further have a substituent include: an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; benzoyl substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group and a phenyl group; a monoalkylamino group having an alkyl group 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 contained in the alkyl group or the substituent group of the phenyl group further have a substituent group, the number of the substituent groups is not limited within the range not hindering the object of the present invention, and is preferably 1 to 4. When the phenyl group, the naphthyl group and the heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different.

R^c2In the case of the carbazolyl group which may have a substituent, the kind of the substituent which the carbazolyl group has is not particularly limited within a range which does not hinder the object of the present invention. As suitable examples of the substituent which the carbazolyl group may have, with R^c1Examples of the substituent in the case of the carbazolyl group which may have a substituent are the same.

From the viewpoint of reactivity of the compound represented by the formula (c1), R is^c2The group represented by the following formula (c2) or the group represented by the following formula (c3) is preferable.

[ solution 10]

In the formula (c2), R^c6And R^c7Are each a monovalent organic group, and b is 0 or 1. In the formula (c3), R^c8Is a group selected from a monovalent organic group, an amino group, a halogen, a nitro group and a cyano group, A is S or O, and c is an integer of 0 to 4.

R in the formula (c2)^c6May be selected from various organic groups within a range not hindering the object of the present invention. As R^c6Suitable examples of (c) include: a hydrogen atom, 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, a heterocyclic carbonyl group which may have a substituent, and the like.

R^c6Among 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 (c2)^c7The 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 suitable as R^c7Specific examples of the group (b) include: a hydrogen atom, 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. As R^c7Among these groups, phenyl groups which may have substituents and naphthyl groups which may have substituents are more preferable, and 2-methylphenyl and naphthyl groups are particularly preferable.

As R^c6Or R^c7When 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, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group, and the like. R^c6Or R^c7In (b) a phenyl groupWhen the naphthyl group and the heterocyclic group further have a substituent, the number of the substituent is not limited within the range not hindering the object of the present invention, and is preferably 1 to 4. R^c6Or 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.

R in the formula (c3)^c8In the case of an organic radical, R^c8May be selected from various organic groups within a range not hindering the object of the present invention. As R in the formula (c3)^c8Suitable 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; benzoyl substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group and a phenyl group; a monoalkylamino group having an alkyl group 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; 2-methylphenylcarbonyl; 4- (piperazin-1-yl) phenylcarbonyl; 4- (phenyl) phenylcarbonyl.

R^c8Among them, benzoyl is preferred; a naphthoyl group; benzoyl substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group and a phenyl group; nitro, more preferably benzoyl; a naphthoyl group; 2-methylphenylcarbonyl; 4- (piperazin-1-yl) phenylcarbonyl; 4- (phenyl) phenylcarbonyl.

In the formula (c3), c is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When c is 1, R^c8Is preferably relative to R^c8The binding site of the bonded phenyl group to the-A-bond is para.

R^c3Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group which may have a substituent. R^c3In the case of a phenyl group which may have a substituent, the substituent which may have a phenyl group and R^c1Is benzene which may have a substituentThe same applies to the radicals. As R^c3Preferably methyl, ethyl or phenyl, more preferably methyl or phenyl.

The oxime ester compound represented by the above formula (c1) can be synthesized, for example, by the following method when a is 0. First, R is reacted with hydroxylamine^c2-CO-R^c1Oximation of the ketone compound to give R^c2-(C＝N-OH)-R^c1An oxime compound represented by the formula. Then, the obtained oxime compound is treated with R^c3Acyl halides represented by-CO-Hal (Hal represents halogen), (R)^c3CO)₂Acylation of the acid anhydride represented by O to obtain an oxime ester compound represented by the above formula (c1) wherein a is 0.

When a is 1, the oxime ester compound represented by the formula (c1) can be synthesized, for example, by the method described below. First, R is reacted in the presence of hydrochloric acid^c2-CO-CH₂-R^c1Reacting the ketone compound with a nitrite to obtain R^c2-CO-(C＝N-OH)-R^c1An oxime compound represented by the formula. Then, the obtained oxime compound is treated with R^c3Acyl halides represented by-CO-Hal (Hal represents halogen), (R)^c3CO)₂Acylation of the acid anhydride represented by O to obtain an oxime ester compound represented by the above formula (c1) wherein a is 1.

Examples of the compound represented by the formula (c1) include a compound represented by the following formula (c 4).

[ solution 12]

In the above formula (c4), a and R^c2And R^c3As described above. R^c9Is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group and a cyano group, and d is an integer of 0 to 4.

In the above formula (c4), R^c9The organic group is not particularly limited as long as it does not inhibit the object of the present invention, and is appropriately selected from various organic groups. As R^c9May be suitable examples ofTo cite: an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, 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, naphthyl which may have a substituent, naphthoxy which may have a substituent, naphthoyl which may have a substituent, naphthoxycarbonyl which may have a substituent, naphthoyloxy which may have a substituent, naphthylalkyl which may have a substituent, heterocyclic group which may have a substituent, amino group substituted with 1 or 2 organic groups, morpholin-1-yl, piperazin-1-yl, halogen, nitro group, cyano group, and the like. When d is an integer of 2 to 4, R^c9May be the same or different. The number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent further included in the substituent.

R^c9In 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^c9In the case of an alkyl group, the alkyl group may be a straight chain or a branched chain. As R^c9Specific 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, and the like. In addition, R^c9In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include: methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, and methoxypropyl, and the like.

R^c9In 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^c9In the case of an alkoxy group, it may be a straight chain or a branched chain. As R^c9In the case of alkoxy groupsSpecific examples thereof include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, sec-pentoxy, tert-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, isooctoxy, sec-octoxy, tert-octoxy, n-nonoxy, isononyloxy, n-decyloxy, and isodecyloxy, and the like. In addition, R^c9In the case of an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include: methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propoxyethoxyethoxy, methoxypropoxy and the like.

R^c9In 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^c9Specific examples of the cycloalkyl group include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, and the like. As R^c9Specific examples of the cycloalkoxy group include: cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy, and the like.

R^c9In 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^c9Specific examples of the saturated aliphatic acyl group include: acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2-dimethylpropionyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, and n-hexadecanoyl, and the like. As R^c9Specific examples of the saturated aliphatic acyloxy group include: acetoxy, propionyloxy, n-butyryloxy, 2-methylpropionyloxy, n-valeryloxy, 2-dimethylpropionyloxy, n-hexanoyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n-undecanoyloxyN-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanoyloxy, n-hexadecanoyloxy, and the like.

R^c9In the case of an alkoxycarbonyl group, the number of carbon atoms is preferably 2 to 20, and more preferably 2 to 7. As R^c9Specific examples of the alkoxycarbonyl group include: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl and the like.

R^c9In the case of phenylalkyl, the number of carbon atoms is preferably 7 to 20, and more preferably 7 to 10. In addition, R^c9In the case of a naphthylalkyl group, the number of carbon atoms is preferably 11 to 20, and more preferably 11 to 14. As R^c9Specific examples of the phenylalkyl group include: benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl. As R^c9Specific examples of the naphthylalkyl group include α -naphthylmethyl group, β -naphthylmethyl group, 2- (α -naphthyl) ethyl group and 2- (β -naphthyl) ethyl group^c9In the case of phenylalkyl or naphthylalkyl, R^c9The phenyl group or naphthyl group may further have a substituent.

R^c9In the case of a heterocyclic group, the heterocyclic group is a five-or six-membered monocyclic ring containing 1 or more N, S, O atoms, or a heterocyclic group in which the monocyclic rings are condensed with each other or with a benzene ring. When the heterocyclic group is a condensed ring, the number of condensed rings is set to 3. 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, iso-thiazoleIndole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, and the like. R^c9In the case of a heterocyclic group, the heterocyclic group may further have a substituent.

R^c9In the case of an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group include: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 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 such suitable organic groups and R^c9Examples 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.

As R^c9When 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, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group, and the like. R^c9Wherein the phenyl group, naphthyl group and heterocyclic group contained in the above-mentioned compound further have a substituentIn the case of the substituent, the number of the substituent is not limited within a range not to impair the object of the present invention, and is preferably 1 to 4. R^c9When 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^c9Among them, from the viewpoint of chemical stability, less steric hindrance, and ease of synthesis of oxime ester compounds, the 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, an alkyl group having 1 to 6 carbon atoms is more preferable, and a methyl group is particularly preferable.

With respect to R^c9Position bonded to phenyl for R^c9When the position of the binding site between the phenyl group and the main skeleton of the oxime ester compound is the 1-position and the position of the methyl group is the 2-position, the phenyl group to be bonded is preferably the 4-position or the 5-position, and more preferably the 5-position. D is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

R in the above formula (c4)^c3Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group which may have a substituent. R^c3Specific examples of (a) are as described for formula (c 1). As R in formula (c4)^c3Methyl, ethyl and phenyl are preferred, and methyl and phenyl are more preferred.

Among the oxime ester compounds, the following compounds are suitable examples of compounds which are contained in formula (c1) but not contained in formula (c 4).

[ solution 13]

Among the oxime ester compounds represented by the formula (c4) which are particularly suitable oxime ester compounds, compounds represented by the following formula are particularly suitable compounds.

[ solution 14]

[ solution 15]

[ solution 16]

[ solution 17]

[ solution 18]

[ solution 19]

[ solution 20]

When the photopolymerization initiator (C) contains an oxime ester compound, the photopolymerization initiator (C) preferably contains only an oxime ester compound, but may contain compounds other than an oxime ester compound. (C) The content of the compound other than the oxime ester compound in the photopolymerization initiator is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less, based on the total mass of the photopolymerization initiator (C).

(C) The content of the photopolymerization initiator is preferably 1 to 15% by mass based on the mass of the solid component in the photosensitive resin composition. By setting the above range, a photosensitive resin composition having both good coatability and curability can be easily prepared.

(D) sunscreen agent

The photosensitive resin composition contains a light-shading agent containing carbon black treated by a silane coupling agent represented by the following formula (1). When the photosensitive resin composition contains carbon black treated with a silane coupling agent represented by the following formula (1) as the light-shielding agent (D), the photosensitive resin composition can easily form a pattern having excellent adhesion to a substrate and excellent insulation properties and in which the reduction in insulation properties due to heating is suppressed. (D) The carbon black contained in the light-shading agent may be treated by combining 2 or more silane coupling agents represented by formula (1).

(D) The light-shading agent may contain a colorant other than carbon black for the purpose of adjusting the color tone and the like within the range not hindering the object of the present invention. (D) The light-shading agent, particularly carbon black, is preferably dispersed using a dispersant. The following description will be given of (D) a light-shading agent, in order of carbon black treatment with a silane coupling agent, a colorant other than carbon black, and a silane coupling agent, and a method of dispersing carbon black.

(silane coupling agent)

(D) The light-shading agent contains carbon black treated by a silane coupling agent represented by the following formula (1).

R¹ _pR² _(3-p)Si-R³-NH-C(O)-Y-R⁴-X…(1)

In the formula (1), R¹Is an alkoxy group. For R¹The alkoxy group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 1 or 2 carbon atoms from the viewpoint of reactivity of the silane coupling agent. As R¹Preferred specific examples of (3) include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy and n-hexoxy.Among these alkoxy groups, methoxy and ethoxy are preferable.

By reacting alkoxy radicals R¹The silanol group formed by hydrolysis reacts with a functional group containing an active hydrogen atom, such as a hydroxyl group or a carboxyl group, present on the surface of the carbon black, and the silane coupling agent is bonded to the surface of the carbon black. Therefore, p is preferably 3 from the viewpoint of facilitating bonding of the silane coupling agent to the surface of the carbon black.

In the formula (1), R²Is an alkyl group. For R²The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 or 2 from the viewpoint of reactivity of the silane coupling agent. As R²Preferred specific examples of (3) include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.

In the formula (1), R³Is an alkylene group. For R³The number of carbon atoms of the alkylene group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 2 to 4. As R³Preferred specific examples of (3) include: methylene, 1, 2-ethylene, 1-ethylene, propane-1, 3-diyl, propane-1, 2-diyl, propane-1, 1-diyl, propane-2, 2-diyl, butane-1, 4-diyl, butane-1, 3-diyl, butane-1, 2-diyl, butane-1, 1-diyl, butane-2, 2-diyl, butane-2, 3-diyl, pentane-1, 5-diyl, pentane-1, 4-diyl, and hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, nonane-1, 9-diyl, decane-1, 10-diyl, Undecane-1, 11-diyl and dodecane-1, 12-diyl. Of these alkylene groups, 1, 2-ethylene, propane-1, 3-diyl and butane-1, 4-diyl are preferable.

Y is-NH-, -O-or-S-, preferably-NH-. This is because the bond represented by-CO-NH-is less susceptible to hydrolysis than the bond represented by-CO-O-or-CO-S-. When a pattern is formed using a photosensitive resin composition containing carbon black treated with a compound having Y — NH —, as a silane coupling agent, the structure of the silane coupling agent is not changed by treatment with an alkali developing solution or the like, and thus a desired effect obtained by using the silane coupling agent can be easily obtained.

R⁴Is a single bond or alkylene group, preferably a single bond. R⁴Preferred examples in the case of alkylene are R³The same is true.

X is a monocyclic or polycyclic nitrogen-containing heteroaryl group which may have a substituent, and-Y-R in X⁴-the bonded ring is a nitrogen-containing six-membered aromatic ring, -Y-R⁴-to a carbon atom in the nitrogen-containing six-membered aromatic ring. Although the reason is not clear, when a photosensitive resin composition containing a compound having such X as a silane coupling agent is used, a cured product having excellent adhesion to a substrate, water resistance, and solvent resistance can be formed.

When X is a polycyclic heteroaryl group, the heteroaryl group may be a group in which a plurality of monocyclic rings are condensed or a group in which a plurality of monocyclic rings are bonded to each other by a single bond. When X is a polycyclic heteroaryl group, the number of rings contained in the polycyclic heteroaryl group is preferably 1 to 3. When X is a polycyclic heteroaryl group, the ring condensed or bonded to the nitrogen-containing six-membered aromatic ring in X may or may not contain a heteroatom, and may or may not be an aromatic ring.

Examples of the substituent that X may have as the nitrogen-containing heteroaryl group include: an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an aliphatic acyl group having 2 to 6 carbon atoms, a benzoyl group, a nitro group, a nitroso group, an amino group, a hydroxyl group, a mercapto group, a cyano group, a sulfonic group, a carboxyl group, a halogen atom, and the like. The number of the substituents of X is not particularly limited within a range not hindering the object of the present invention. The number of substituents of X is preferably 5 or less, more preferably 3 or less. When X has a plurality of substituents, the plurality of substituents may be the same or different.

Preferred examples of X include groups represented by the following formulae.

[ solution 21]

Among the above groups, X is more preferably a group represented by the following formula.

[ solution 22]

As a suitable specific example of the compound represented by the formula (1) described above, the following compounds 1 to 8 can be mentioned.

[ solution 23]

(carbon Black)

The carbon black is not particularly limited as long as it does not inhibit the object of the present invention, and can be appropriately selected from known carbon blacks. As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used.

Further, carbon black subjected to treatment for introducing an acidic group is preferably used. When a photosensitive resin composition containing an acidic group-introduced carbon black as the light-shielding agent (D) is used, there is an advantage that a pattern having excellent insulation properties is easily formed, but there is a disadvantage that a fine pattern having excellent adhesion to a substrate is hardly formed. However, the above-mentioned problem concerning the adhesion of the pattern to the substrate can be solved by treating the carbon black having an acidic group introduced thereto with the silane coupling agent represented by the above formula (1).

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: carboxyl group, sulfonic group, phosphoric group, etc. The acidic groups introduced into the carbon black may form salts. The cation which forms a salt with an acidic group is not particularly limited insofar as it does not hinder the object of the present invention. Examples of cations include: various metal ions, cations of nitrogen-containing compounds, ammonium ions, and the like, and alkali metal ions such as sodium ions, potassium ions, lithium ions, and the like, 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 a carboxylic acid group, a carboxylate group, a sulfonic acid group and a sulfonate group are preferable.

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, or the like, or an indirect substitution method using sulfite, bisulfite, or the like.

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

3) A method for reacting an organic compound having a halogen atom and an acidic group with carbon black having a hydroxyl group by the Williams' etherification method.

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

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

Among these methods, method 2) is preferred from the viewpoint of easy handling 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 compounds include: aminobenzoic acids such as aminobenzenesulfonic acid and 4-aminobenzoic acid.

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

The carbon black may be subjected to coating treatment with a resin. When a photosensitive resin composition containing carbon black coated with a resin is used, a pattern having excellent light-shielding properties and insulating properties and low surface reflectance can be easily formed. Examples of resins that can be used for coating carbon black include: thermosetting resins such as phenol resins, melamine resins, xylene resins, diallyl phthalate resins, glyphosate 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, polyether sulfone, polyphenylene sulfone, polyarylate, and polyether ether ketone. When the total amount of the carbon black and the resin is 100 parts by mass, the coating amount of the resin with respect to the carbon black is preferably 1 to 30 parts by mass.

(coloring agent other than carbon Black)

For the purpose of adjusting the color tone, the light-shading agent (D) may contain a black pigment other than carbon black, and a colored pigment such as red, blue, green, yellow, or violet together with the carbon black. Examples of black pigments other than carbon black include: metal oxides, composite oxides, metal sulfides, metal sulfates, metal carbonates, and the like of perylene pigments, silver-tin alloys, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, and the like. The amount of the colorant other than carbon black is preferably 15 parts by mass or less, and more preferably 10 parts by mass or less, based on 100 parts by mass of the total amount of the light-shading agent (D).

(treatment of carbon Black with silane coupling agent)

The method of treating the carbon black with the silane coupling agent is not particularly limited as long as the object of the present invention is not impaired. Typically, a method of reacting carbon black with a silane coupling agent in the presence of water in an organic solvent in which the silane coupling agent is soluble is preferred.

Examples of the organic solvent that can be suitably used for the treatment of carbon black with a silane coupling agent include: monovalent alkyl alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 3-propanediol, isopropylene glycol, polypropylene glycol, pentanediol, propylene glycol, butanediol, isobutylene glycol, thiodiethylene glycol, 1, 2-hexanediol, 1, 6-hexanediol, 2-ethyl-1, 3-hexanediol, 1, 2-pentanediol, 1, 5-pentanediol, 2-methyl-2, 4-pentanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 7-heptanediol, 1, 8-octanediol, 2-butene-1, 4-diol, and glycerol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monophenyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monoisopropyl ether; ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, propylene glycol monopropyl ether acetate, ethylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, and mixtures thereof, Glycol ether esters such as 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate and 4-methyl-4-methoxypentyl acetate; ketone solvents such as acetone, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone. The amount of the organic solvent to be used is not particularly limited as long as the treatment liquid containing carbon black and the silane coupling agent can be easily stirred. The amount of the organic solvent used is preferably such that the solid content concentration of the treatment liquid containing carbon black and the silane coupling agent is 5 to 60 mass%.

The amount of the silane coupling agent to be used is not particularly limited as long as the desired effect can be obtained. The amount of the silane coupling agent is preferably 0.5 to 15 parts by mass, and more preferably 3 to 7 parts by mass, per 100 parts by mass of the carbon black.

The treatment of carbon black with a silane coupling agent is carried out in the presence of water. Water may be added to the treatment liquid containing the carbon black and the silane coupling agent, but it is not necessarily required to add water to the treatment liquid. When the treatment with the silane coupling agent is performed in an air atmosphere containing sufficient moisture, the alkoxy group of the silane coupling agent is hydrolyzed by the moisture in the air to form a silanol group.

The temperature at which the carbon black is treated with the silane coupling agent is not particularly limited as long as the reaction between the silane coupling agent and the carbon black is favorably carried out. The treatment of carbon black with the silane coupling agent is typically preferably performed at 25 to 100 ℃, more preferably at 40 to 60 ℃.

After the carbon black is treated with the silane coupling agent according to the above-mentioned method, the suspension of the carbon black obtained after the treatment can be used as it is for (D) a dispersion of a light-shading agent or for the preparation of a photosensitive resin composition. The suspension of carbon black obtained after the treatment may be dried, and the obtained powdered carbon black may be used for (D) the dispersion of the light-shielding agent or the preparation of the photosensitive resin composition.

When the light-shading agent (D) contains a colorant other than carbon black, the colorant other than carbon black may be treated with the silane coupling agent represented by formula (1) in the same manner as carbon black. Further, (D) a light-shading agent which is a mixture of carbon black and a colorant other than carbon black may be treated with a silane coupling agent.

(method of dispersing carbon Black)

As described above, the carbon black contained in the light-shading agent (D) is preferably dispersed using a dispersant. The carbon black dispersed with the dispersant is generally used in the form of a dispersion liquid obtained by dispersing the carbon black with the dispersant in a dispersion medium. The method for producing the dispersion of carbon black is not particularly limited, and the dispersion can be produced by a conventionally known method for producing dispersions of various pigments.

A suitable example of the method for producing the dispersion liquid is a method of treating a suspension containing a dispersion medium, carbon black, and a dispersant using a known dispersing apparatus. Hereinafter, a method for producing the carbon black dispersion, a dispersant, a dispersion medium, and other components that the carbon black dispersion may contain will be described.

[ method for producing carbon Black Dispersion ]

As a dispersing device used for the dispersion treatment of carbon black, various dispersing devices conventionally used for the dispersion of pigments can be used. Specific examples of suitable dispersing apparatuses include: kneaders, salt milling treatment kneaders, roll mills, planetary mixers, paint mixers, ball mills, sand mills, attritors, bead mills, annular gap ball mills, homomixers, homogenizers, wet jet mills, high pressure homogenizers, ultrasonic homogenizers, and the like. When a medium is used as the dispersion device, glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads, or the like can be used as the medium.

When the dispersion treatment is carried out by an ultrasonic homogenizer, it is preferable to use carbon black which has been previously subjected to dispersion by the above-mentioned kneader, salt mill treatment kneader, roll mill, planetary mixer, homomixer, homogenizer, wet jet mill, high pressure homogenizer, bead mill, and the like.

[ dispersing agent ]

The type of the dispersant is not particularly limited as long as the carbon black can be dispersed well. Various dispersants conventionally used for pigment dispersion can be used as the dispersant. Suitable examples of the dispersant include polymer dispersants such as polyethyleneimine-based polymer dispersants, urethane resin-based polymer dispersants, and acrylic resin-based polymer dispersants, and pigment derivatives. The polymer dispersant and the pigment derivative are used in the same amounts as those used in the conventional pigment dispersion treatment.

Further, it is also preferable to disperse the carbon black using a dispersant containing polyamic acid. In the case of using a photosensitive resin composition containing (D) a light-shading agent containing carbon black dispersed with a dispersant containing polyamic acid, a pattern in which the decrease in insulation due to heating is suppressed is easily formed.

It is considered that the molecular chain of the polyamic acid is bound to the surface of the carbon black primary particle at a point by an interaction such as a hydrogen bond or an intermolecular force with the surface of the carbon black. Therefore, it is considered that the molecular chain of the polyamic acid acts as a spacer on the surface of the primary particle of the carbon black, and promotes the dispersion of the carbon black and stabilizes the dispersion. Therefore, in the photosensitive resin composition containing the light-shielding agent (D) containing carbon black dispersed using polyamic acid as a dispersant, aggregation of carbon black is less likely to occur.

The molecular weight of the polyamic acid is preferably 5,000 to 30,000 in terms of mass average molecular weight, and more preferably 10,000 to 20,000. When the molecular weight of the polyamic acid is within the above range, the carbon black can be dispersed well.

The amount of the polyamic acid used is not particularly limited as long as the carbon black is well dispersed. From the viewpoint of ease of dispersion of carbon black, the polyamic acid is preferably used in an amount of 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, based on 100 parts by mass of carbon black.

Examples of suitable polyamic acids include polyamic acids containing a structural unit represented by the following formula (D1).

[ solution 24]

(in the formula (D1), R^d1Is a tetravalent organic radical, R^d2Is a divalent organic group, and n is the number of repetitions of the constituent unit represented by formula (D1). )

In the formula (D1), R^d1And R^d2Are respectively provided withThe organic group is a tetravalent organic group, and the number of carbon atoms is preferably 2 to 50, more preferably 2 to 30. R^d1And R^d2Each of which may be an aliphatic group, an aromatic group, or a group having a combination of these structures. R^d1And R^d2Halogen atoms, oxygen atoms, and sulfur atoms may be contained in addition to carbon atoms and hydrogen atoms. R^d1And R^d2When an oxygen atom, a nitrogen atom or a sulfur atom is contained, the oxygen atom, the nitrogen atom or the sulfur atom may be selected from the group consisting of a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N-, -CH-N-, -COO-, -O-, -CO-, -SO-and₂the radicals-S, -S-and-S-are contained in R^d1And R^d2Among them, more preferably selected from-O-, -CO-, -SO-, -SO₂The radicals-S, -S-and-S-are contained in R^d1And R^d2In (1).

The polyamic acid is generally prepared by reacting a tetracarboxylic dianhydride component with a diamine component. The tetracarboxylic dianhydride component, the diamine component, and the method for producing polyamic acid will be described below.

Tetracarboxylic dianhydride component

The tetracarboxylic dianhydride component used as a raw material for synthesizing the polyamic acid is not particularly limited as long as it is a compound capable of reacting with the diamine component to form the polyamic acid. The tetracarboxylic dianhydride component can be appropriately selected from tetracarboxylic dianhydrides which have been conventionally used as raw materials for synthesizing polyamic acids. The tetracarboxylic dianhydride component may be an aromatic tetracarboxylic dianhydride, or may be an aliphatic tetracarboxylic dianhydride, and is preferably an aromatic tetracarboxylic dianhydride. The tetracarboxylic dianhydride component may be used in combination of 2 or more.

Suitable specific examples of the aromatic tetracarboxylic dianhydride include: pyromellitic dianhydride, 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride, 2,3,3 ', 4 ' -biphenyltetracarboxylic dianhydride, 3,3 ', 4,4 ' -benzophenonetetracarboxylic dianhydride, 4,4 ' -oxydiphthalic anhydride, and 3,3 ', 4,4 ' -diphenylsulfonetetracarboxylic dianhydride. Among these, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferred from the viewpoint of cost, ease of use, and the like.

Diamine component

The diamine component used as a raw material for synthesizing the polyamic acid is not particularly limited as long as it is a compound capable of reacting with the tetracarboxylic dianhydride component to form the polyamic acid. The diamine component can be appropriately selected from diamines which have been conventionally used as raw materials for synthesizing polyamic acid. The diamine component may be an aromatic diamine or an aliphatic diamine, and is preferably an aromatic diamine. The diamine component may be used in combination of 2 or more.

Suitable specific examples of the aromatic diamine include: p-phenylenediamine, m-phenylenediamine, 2, 4-diaminotoluene, 4 ' -diaminobiphenyl, 4 ' -diamino-2, 2 ' -bis (trifluoromethyl) biphenyl, 3 ' -diaminodiphenyl sulfone, 4 ' -diaminodiphenyl sulfide, 4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenyl ether, 3 ' -diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 4 ' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] sulfone, p-phenylenediamine, 4-diaminodiphenyl sulfone, Bis [4- (3-aminophenoxy) phenyl ] sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] propane, and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane. Among these, p-phenylenediamine, m-phenylenediamine, 2, 4-diaminotoluene, and 4, 4' -diaminodiphenyl ether are preferable from the viewpoints of cost, ease of handling, and the like.

Method for producing Polyamic acid

The tetracarboxylic dianhydride component and the diamine component described above are reacted in a solvent capable of dissolving both components, thereby obtaining a polyamic acid. The amounts of the tetracarboxylic dianhydride component and the diamine component used in the synthesis of the polyamic acid are not particularly limited. The diamine component is preferably used in an amount of 0.50 to 1.50 mol, more preferably 0.60 to 1.30 mol, and particularly preferably 0.70 to 1.20 mol, based on 1 mol of the tetracarboxylic dianhydride component.

Examples of the solvent that can be used for the synthesis of the polyamic acid include: aprotic polar organic solvents such as N, N' -tetramethylurea, N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, hexamethylphosphoramide, 1, 3-dimethyl-2-imidazolidinone, and γ -butyrolactone; glycol ethers such as diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, and propylene glycol monoalkyl ether propionate. These solvents may be used in combination of 2 or more. Among these, N' -tetramethylurea is preferably used.

The amount of the solvent used in the synthesis of the polyamic acid is not particularly limited as long as the polyamic acid having a desired molecular weight can be synthesized. Typically, the amount of the solvent is preferably 100 to 4000 parts by mass, more preferably 150 to 2000 parts by mass, based on 100 parts by mass of the total amount of the tetracarboxylic dianhydride component and the diamine component.

The temperature at which the tetracarboxylic dianhydride component and the diamine component are reacted is not particularly limited as long as the reaction proceeds well. Typically, the reaction temperature of the tetracarboxylic dianhydride component and the diamine component is preferably-5 to 150 ℃, more preferably 0 to 120 ℃, and particularly preferably 0 to 70 ℃. The time for reacting the tetracarboxylic dianhydride component and the diamine component varies depending on the reaction temperature, but is typically preferably 1 to 50 hours, more preferably 2 to 40 hours, and particularly preferably 5 to 30 hours.

[ dispersing Medium ]

The dispersion medium for dispersing the carbon black is not particularly limited as long as the carbon black can be dispersed well. The dispersion medium may be a liquid medium conventionally used as a dispersion medium for dispersing carbon black, and may be appropriately selected from dispersing agent-soluble media. Typically, polar organic solvents are preferred as the dispersion medium. The dispersion medium may contain water in the range where the dispersant is soluble.

Suitable specific examples of the dispersion medium include: water; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 3-propanediol, isopropylene glycol, polypropylene glycol, pentanediol, trimethylene glycol, butanediol, isobutylene glycol, thiodiethylene glycol, 1, 2-hexanediol, 1, 6-hexanediol, 2-ethyl-1, 3-hexanediol, 1, 2-pentanediol, 1, 5-pentanediol, 2-methyl-2, 4-pentanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 7-heptanediol, 1, 8-octanediol, 2-butene-1, 4-diol, and glycerol; polyhydric alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monophenyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monoisopropyl ether; ketones such as acetonylacetone; esters such as gamma-butyrolactone, diacetin, triethyl phosphate, etc.; lower alkoxyalcohols such as 2-methoxyethanol and 2-ethoxyethanol; amines such as ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, triethylenetetramine, tetraethylenepentamine and pentamethyldiethylenetriamine; amides such as formamide, N-dimethylformamide, N-methylformamide, and N, N-dimethylacetamide; ureas such as N, N '-tetramethylurea and N, N' -tetraethylurea; heterocyclic compounds such as 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, morpholine, N-ethylmorpholine, 2-oxazolidinone, 1, 3-dimethyl-2-imidazolidinone, imidazole, methylimidazole, hydroxyimidazole, dimethylaminopyridine, 1, 3-propanesultone, hydroxyethylpiperazine, and piperazine; sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane. The solvent other than N, N '-tetramethylurea described above may be contained in a combination of 2 or more in the solvent containing N, N' -tetramethylurea.

The dispersion medium described above is preferably an organic solvent containing N, N' -tetramethylurea. Carbon black can be dispersed rapidly and satisfactorily in an organic solvent containing N, N' -tetramethylurea by dispersing the carbon black using a polyamic acid as a dispersant.

The content of N, N '-tetramethylurea in the organic solvent containing N, N' -tetramethylurea is not particularly limited as long as the dispersion state of the carbon black is maintained well. Typically, the content of N, N '-tetramethylurea in the organic solvent containing N, N' -tetramethylurea 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.

The content of the dispersion medium in the carbon black dispersion liquid is not particularly limited as long as the dispersion state of the carbon black is kept good. The carbon black dispersion liquid usually contains a dispersion medium in such an amount that the solid content concentration of the carbon black dispersion liquid becomes 5 to 60 mass%, preferably 20 to 40 mass%.

[ other ingredients ]

The carbon black dispersion may contain various additives conventionally blended in carbon black dispersions. Examples of such additives include: viscosity modifiers, surfactants, antioxidants, ultraviolet absorbers, pH modifiers, and defoamers. These additives may be used in the same amount as that of the conventional additives to be added to the carbon black dispersion within a range not adversely affecting the properties of the carbon black dispersion.

The content of the light-shading agent (D) in the photosensitive resin composition may be appropriately selected within a range not hindering the object of the present invention, and is typically preferably 25 to 70 mass%, more preferably 30 to 65 mass%, and particularly preferably 35 to 60 mass% with respect to the total solid content of the photosensitive resin composition. By using the light-shading agent in an amount within the above range, the black matrix or the black columnar spacer formed using the photosensitive resin composition can have good light-shielding properties, and the exposure failure and curing failure during exposure of the photosensitive resin composition can be easily suppressed.

< (E) light absorber

The photosensitive resin composition may contain a light absorbing agent. The light absorber is not particularly limited, and a compound capable of absorbing exposure light can be used, and particularly a compound capable of absorbing light in a wavelength region of 200 to 450nm is preferable. Examples thereof include: naphthalene compounds, dinaphthalene compounds, anthracene compounds, phenanthroline compounds, dyes, and the like.

Specific examples thereof include cinnamic acid derivatives such as 2-ethylhexyl cinnamate, 2-ethylhexyl p-methoxycinnamate, isopropyl methoxycinnamate and isoamyl methoxycinnamate, naphthalene derivatives such as α -naphthol, β -naphthol, α -naphthol methyl ether, α -naphthol ethyl ether, 1, 2-dihydroxynaphthalene, 1, 3-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene and 2, 7-dihydroxynaphthalene, anthracene and derivatives thereof such as 9, 10-dihydroxyanthracene, cinnamic acid derivatives and naphthalene derivatives thereof, and particularly preferably cinnamic acid derivatives and naphthalene derivatives thereof, and these light absorbers are used alone or in combination of 2 or more.

(E) The content of the light absorber is preferably 0.5 to 20 parts by mass per 100 parts by mass of the solid content of the photosensitive resin composition. By setting the range, the ratio of the change in film thickness when the exposure amount is changed can be increased while maintaining the breakdown strength after curing satisfactorily.

(S) organic solvent

The photosensitive resin composition preferably contains an organic solvent for dilution. Examples of the organic solvent include: (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl 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, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc.; (poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl 2-oxobutyrate and other esters; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.

Among them, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, the above-mentioned other ethers, alkyl lactates, and the above-mentioned other esters are preferable, and alkylene glycol monoalkyl ether acetates, the above-mentioned other ethers, and the above-mentioned other esters are more preferable. These solvents may be used alone or in combination of 2 or more.

The content of the (S) organic solvent is preferably such that the solid content concentration of the photosensitive resin composition becomes 1 to 50% by mass, more preferably 5 to 30% by mass.

< other ingredients >

The photosensitive resin composition of the present invention may contain various additives as required. Examples of the additives include: sensitizers, curing accelerators, fillers, adhesion promoters, antioxidants, anti-agglomeration agents, thermal polymerization inhibitors, defoamers, surfactants, and the like.

The adhesion promoter is preferably a silane coupling agent. By adding a silane coupling agent to the photosensitive resin composition independently of the silane coupling agent represented by formula (1) used for the treatment of carbon black, a photosensitive resin composition capable of forming a pattern having extremely excellent adhesion to a substrate can be obtained.

The silane coupling agent used as the adhesion promoter may be the silane coupling agent represented by formula (1) described above or a silane coupling agent other than the silane coupling agent represented by formula (1).

Suitable examples of the silane coupling agent other than the silane coupling agent represented by formula (1) include: n-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine.

Method for Forming patterned cured Material

The method for forming a patterned cured product of the present invention comprises: a step of coating the photosensitive resin composition on a substrate to form a coating film; a step of exposing the formed coating film with position selectivity according to the shape of the pattern; and a step of developing the exposed coating film.

First, in the step of forming a coating film, a photosensitive resin composition is applied to a substrate on which a patterned cured product 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 rotary machine (rotary coating apparatus) or a curtain coater. After coating, the solvent is removed by drying as necessary, thereby forming a coating film.

Next, the coating film is irradiated with an active energy ray such as ultraviolet ray or excimer laser through a negative mask, and the coating film is partially exposed in accordance with the shape of the pattern. In the exposure, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a UV lamp,carbon arc lamps and the like emit ultraviolet light. The exposure amount varies depending on the composition of the photosensitive resin composition, and is preferably, for example, 10 to 600mJ/cm²Left and right.

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

Subsequently, the coating film subjected to the position-selective exposure is developed with a developer, thereby forming a cured product. The developing method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developing solution 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.

Then, the insoluble portion of the developed coating film is post-baked as necessary to form a patterned cured product. The post-baking is preferably carried out at 150 to 250 ℃ for 15 to 60 minutes.

The cured product thus formed is excellent in adhesion to a substrate and insulation properties, and is suppressed in the reduction of insulation properties due to heat, and therefore, is suitable for use as a black matrix or a black columnar spacer in various display devices.

Examples

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

Examples 1 to 14 and comparative examples 1 to 8

The photosensitive resin compositions of examples and comparative examples were obtained by uniformly mixing 114 parts by mass of an alkali-soluble resin (solid content concentration: 55% by mass, solvent: 3-methoxybutyl acetate), 25 parts by mass of a photopolymerizable monomer, 12 parts by mass of a photopolymerization initiator, and carbon black dispersions in the amounts shown in Table 1, and then diluting the mixture with an organic solvent so that the solid content concentration became 15% by mass.

As the organic solvent for dilution, a mixed solvent of 3-Methoxybutyl Acetate (MA), propylene glycol monomethyl ether acetate (PM), and cyclohexanone (AN) (mixing ratio (mass ratio) MA/PM/AN: 60/20/20) was used.

As the carbon black dispersion, a dispersion obtained by dispersing carbon black of the type shown in table 1 treated with a silane coupling agent shown in table 1 with a dispersant shown in table 1 was used.

In addition, in example 13 and 14 and comparative examples 5 and 6 of the photosensitive resin composition further adding table 1 types of adhesion promoter 3 parts by mass.

Details of the material for producing the photosensitive resin composition will be described later.

[ Table 1]

The following describes a carbon black dispersion, an alkali-soluble resin, a photopolymerizable monomer and a photopolymerization initiator for producing a photosensitive resin composition.

(carbon Black Dispersion)

In the preparation of the carbon black dispersion, the following carbon blacks CB and CB-A were used.

CB: carbon black (manufactured by Regal 250R, Cabot Co.)

CB-A: carbon black subjected to the treatment of introducing an acidic group was prepared in the following manner.

The silane coupling agents used for the treatment of carbon black were SC-A, SC-B and SC-C described below. Among the silane coupling agents described below, SC-A and SC-C are also used as adhesion promoters.

[ solution 25]

When carbon black is treated with a silane coupling agent, the treatment with the silane coupling agent is performed in the following manner.

[ preparation example of CB-A ]

550g of carbon black CB (manufactured by Regal 250R, Cabot Co.), 31.5g of sulfanilic acid and 1000g of ion-exchanged water were charged into a reaction vessel equipped with a jacket and a stirring device, the jacket temperature of which was set to 60 ℃. After a solution prepared by dissolving 12.6g of sodium nitrite in 100g of deionized water was charged into a Brownian (ブラウ) stirrer, the mixture in the stirrer was stirred at 60 ℃ for 2 hours at 50 rpm to conduct a diazo coupling reaction. After stirring, the contents of the stirrer were cooled to room temperature. Next, the carbon black contained in the contents of the stirrer was purified by a diafiltration method using deionized water. No benzenesulfonic acids derived from sulfanilic acid were detected in the washing water, and it was found that a benzenesulfonic acid group was introduced into carbon black by the diazo coupling reaction. The purified carbon black was dried at 75 ℃ overnight and then pulverized to obtain a carbon black (CB-A) having a benzenesulfonic acid group introduced therein.

[ silane coupling agent treatment ]

50g of carbon black of the type shown in Table 1 and 200g of an isopropyl alcohol solution of a silane coupling agent containing the silane coupling agent of the type shown in Table 1 at a concentration of 1% by mass were mixed and stirred at 60 ℃ for 3 hours. The stirred suspension containing carbon black was heated to 100 ℃ to volatilize isopropanol and methanol produced as a by-product, thereby obtaining carbon black powder treated with a silane coupling agent.

As the dispersant, ｃA carbon black dispersion was prepared in the following manner using the following DP-A and DP-B.

DP-A: urethane polymer dispersant (BYK-167, manufactured by BYK corporation, Japan)

DP-B: polyamic acid (1/1 (molar ratio) reactant of pyromellitic dianhydride (PMDA) and 4, 4' -diaminodiphenyl ether (ODA), mass-average molecular weight: 14000)

[ preparation examples of carbon Black Dispersion ]

20g of carbon black which was untreated or treated with a silane coupling agent of the type shown in Table 1, 3g of a dispersant of the type shown in Table 1, and 50g of 3-methoxybutyl acetate were mixed. The resulting mixed solution was stirred to disperse the carbon black. Subsequently, the suspension containing the dispersed carbon black was diluted with 3-methoxybutyl acetate to a solid content concentration of 22 mass%, to obtain a carbon black dispersion.

(alkali-soluble resin)

As the alkali-soluble resin, the following A-1 was used.

A-1: a resin (solid content: 55%, solvent: 3-methoxybutyl acetate) was obtained by the following method

[ Synthesis example of alkali-soluble resin ]

First, 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 were put into a 500ml four-necked flask, 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 raised while the solution was cloudy, and the solution was heated to 120 ℃ to completely dissolve the compound. At this time, the solution gradually became transparent and viscous, and stirring was continued in this state. During this time, the acid value was measured, and stirring with heating was continued until the acid value was less than 1.0 mgKOH/g. It took 12 hours until the acid value reached the target value. Then, the mixture was cooled to room temperature, and a bisphenol fluorene type epoxy acrylate represented by the following formula (a-4) was obtained as a colorless transparent solid.

[ solution 26]

Then, to 307.0g of the bisphenol fluorene type epoxy acrylate obtained in the above manner was added 600g of 3-methoxybutyl acetate and dissolved, and then 80.5g of benzophenone tetracarboxylic dianhydride and 1g of tetraethylammonium bromide were mixed, slowly heated, and reacted at 110 to 115 ℃ for 4 hours. 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 resin (A-1). Disappearance of the acid anhydride group was confirmed by IR spectroscopy.

The resin (A-1) corresponds to the resin represented by the above formula (a-1).

(photopolymerizable monomer)

DPHA: dipentaerythritol hexaacrylate

(photopolymerization initiator)

OXE 02: ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ],1- (O-acetyloxime) (IRGACURE OXE02, manufactured by BASF)

The obtained patterned cured products formed using the photosensitive resin compositions of the examples and comparative examples were evaluated for the adhesion to thin lines, the initial surface resistance, and the surface resistance after heat treatment, according to the following methods. The results of these evaluations are shown in Table 2.

[ evaluation of adhesion of thin line ]

A photosensitive resin composition was applied onto a glass substrate (100mm × 100mm) by a spin coater, and then prebaked at 90 ℃ for 120 seconds to form a coating film having a film thickness of 1.0. mu.m.Next, a mirror projection alignment aligner (product name: TME-150RTO, manufactured by TOPCON corporation) was used to set an exposure gap to 50 μm and to set the gap to 30mJ/cm through a negative mask²The exposure amount of (a) irradiating ultraviolet rays to the coating film, wherein the negative mask is designed to: a Line-and-space pattern (ラインアンドスペース: Line-and-space) having 16 lines each having a width of 1 μm from 5 μm to 20 μm was formed. The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26 ℃ for 50 seconds, and then post-baked at 230 ℃ for 30 minutes, thereby forming a line-and-space pattern.

The formed line-and-space pattern was observed with an optical microscope, and adhesion of the thin line was evaluated according to the following criteria.

◎ No peeling was observed across the full width of the line.

○ peeling was observed in the lines having widths of 5 μm and 6 μm, but peeling was not observed in the lines having widths of 7 μm or more.

△ peeling was observed in the case of the lines having a width of 5 to 8 μm, but peeling was not observed in the case of the lines having a width of 9 μm or more.

× peeling is observed in the line with width of 5-12 μm.

[ evaluation of initial surface resistance and surface resistance after Heat treatment ]

A coating film having a film thickness of 1.0 μm was formed on a glass substrate (100mm × 100mm) in the same manner as for the evaluation of the thin line adhesion, and then, the coating film was irradiated with ultraviolet light through a photomask with an exposure gap of 50 μm using a mirror projection aligner (product name: TME-150RTO, manufactured by TOPCON K.) and with an exposure amount of 100mJ/cm². The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26 ℃ for 50 seconds, and then post-baked at 230 ℃ for 30 minutes to produce a cured film. The surface resistance value of the cured film was measured as the initial surface resistance. The cured film was post-baked at 230 ℃ for 3 hours, and the surface resistance value of the cured film after the further heat treatment was measured as the surface resistance after the heat treatment.

[ Table 2]

According to examples 1 to 14, it can be seen that: when a photosensitive resin composition containing (a) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a light-shielding agent containing carbon black treated with a silane coupling agent having a predetermined structure represented by formula (1) is used, a black pattern having excellent adhesion to a substrate and excellent insulation properties and having insulation properties that are not easily degraded by heating can be formed.

From the comparison between examples 1 to 4 and examples 5 to 8: (D) when the light-shading agent contains carbon black obtained by treating carbon black subjected to the treatment of introducing an acidic group with the silane coupling agent, a black pattern having excellent insulation properties is easily formed.

According to the comparison between example 2 and example 4 and the comparison between example 6 and example 8, it can be seen that: (D) when the light-blocking agent contains carbon black dispersed using polyamic acid as a dispersant, it is particularly easy to suppress the decrease in insulation properties of the formed black pattern due to heating.

From a comparison of example 2 with examples 13 and 14: when the photosensitive resin composition further contains a silane coupling agent as an adhesion promoter, independently of the silane coupling agent used for the treatment of carbon black, a black pattern having particularly excellent adhesion to a thin line can be formed.

From comparative examples 1,2, 5 and 6: when a photosensitive resin composition containing (a) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a light-shielding agent containing carbon black to which treatment for introducing an acidic group and treatment with a silane coupling agent have not been applied is used, a black pattern having poor insulation properties is formed.

From comparative examples 3 and 4, it can be seen that: when a photosensitive resin composition containing (a) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a light-shielding agent containing carbon black subjected to treatment for introducing an acidic group but not subjected to treatment with a silane coupling agent is used, a black pattern having excellent insulation properties but remarkably poor adhesion properties is formed.

From a comparison of comparative example 2 and comparative example 7, it can be seen that: even when the carbon black contained in the light-shading agent (D) is treated with a silane coupling agent having a structure other than formula (1), the insulating properties of the black pattern formed cannot be improved.

From a comparison of comparative example 4 and comparative example 8, it can be seen that: (D) when the light-shading agent contains carbon black subjected to treatment for introducing an acidic group, even if the carbon black is treated with a silane coupling agent having a structure other than formula (1), the insulating property of the formed black pattern cannot be improved.

Claims

1. A photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator and (D) a light-shading agent,

the light-shading agent (D) comprises carbon black treated with a silane coupling agent represented by the following formula (1),

R¹ _pR² _(3-p)Si-R³-NH-C(O)-Y-R⁴-X…(1)

in the formula (1), R¹Is alkoxy, R²Is alkyl, p is an integer of 1 to 3, R³Is alkylene, Y is-NH-, R⁴Is a single bond, X is with or withoutSubstituted, monocyclic or polycyclic, nitrogen-containing heteroaryl, of which X is substituted with-Y-R⁴-the bonded ring is a nitrogen-containing six-membered aromatic ring, -Y-R⁴-to a carbon atom in said nitrogen-containing six-membered aromatic ring.

2. The photosensitive resin composition according to claim 1, wherein the carbon black is a carbon black treated with the silane coupling agent represented by the formula (1) in the absence of the alkali-soluble resin (A).

3. The photosensitive resin composition according to claim 1, wherein the treatment is carried out by allowing an alkoxy group R of the silane coupling agent represented by the formula (1) to have¹A treatment of reacting the silanol group formed by hydrolysis with a functional group containing an active hydrogen atom present on the surface of the carbon black.

4. The photosensitive resin composition according to claim 1, wherein the treatment is a treatment of bonding the silane coupling agent to the surface of carbon black.

5. The photosensitive resin composition according to claim 1, wherein the carbon black is a carbon black obtained by treating a carbon black subjected to an acid group-introducing treatment with the silane coupling agent.

6. The photosensitive resin composition according to claim 5, wherein the carbon black subjected to the treatment of introducing an acidic group has 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.

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the carbon black is dispersed using a dispersant containing a polyamic acid.

8. The photosensitive resin composition according to claim 1, wherein the content of the carbon black subjected to the surface treatment with the silane coupling agent is 25 to 70% by mass based on the mass of the solid content in the photosensitive resin composition.

9. A method of forming a patterned cured article, comprising:

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

a step of exposing the coating film with position selectivity; and

and developing the exposed coating film.

10. A patterned cured product formed by using the photosensitive resin composition according to claim 1.

11. The patterned cured product according to claim 10, which is a black matrix or black columnar spacers.

12. A display device comprising a black matrix or a black columnar spacer formed using the photosensitive resin composition according to claim 1.

13. A carbon black which is treated with a silane coupling agent represented by the following formula (1),

R¹ _pR² _(3-p)Si-R³-NH-C(O)-Y-R⁴-X…(1)

in the formula (1), R¹Is alkoxy, R²Is alkyl, p is an integer of 1 to 3, R³Is alkylene, Y is-NH-, R⁴Is a single bond, X is a monocyclic or polycyclic nitrogen-containing heteroaryl group which may or may not have a substituent, and-Y-R in X⁴-the bonded ring is a nitrogen-containing six-membered aromatic ring, -Y-R⁴-to a carbon atom in said nitrogen-containing six-membered aromatic ring.

14. The carbon black according to claim 13, which is treated with the silane coupling agent represented by the formula (1) in the absence of (A) an alkali-soluble resin.

15. The carbon black according to claim 13, wherein the treatment is carried out so that the silane coupling agent represented by the formula (1) has an alkoxy group R¹A treatment of reacting the silanol group formed by hydrolysis with a functional group containing an active hydrogen atom present on the surface of the carbon black.

16. The carbon black of claim 13, wherein the treatment is a treatment that bonds the silane coupling agent to the surface of the carbon black.