JP2017187717A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that can suppress crystallization of a resin having a cardo structure and allows formation of a smooth cured film, a cured film made of a cured product of the photosensitive resin composition, and a method for forming a cured film using the photosensitive resin composition.SOLUTION: The photosensitive resin composition comprises (A) an alkali-soluble resin comprising a resin having a cardo structure, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (S) a solvent, in which (L) a low boiling point solvent having a boiling point of lower than 180°C under atmospheric pressure and (H) a high boiling point solvent having a boiling point of 180°C or higher and 300°C or lower under atmospheric pressure are used each in a predetermined amount as the (S) solvent. The (H) high boiling point solvent contains a compound having an aromatic hydrocarbon ring and an ester bond.SELECTED DRAWING: None

Description

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

  In display devices such as liquid crystal display devices and organic EL display devices, various curable compositions such as transparent or colored insulating materials are used. Examples of the colored insulating material include a black column spacer for keeping a distance (cell gap) between two substrates constant, a black matrix for partitioning a colored region in a color filter, and the like. .

As a method for forming an insulating material used in such a panel for a display device, for example, a method using a negative photosensitive resin composition has been proposed.
Specifically, use of a negative photosensitive resin composition including a photopolymerizable compound, a photopolymerization initiator, an acrylic resin fine particle dispersion in which acrylic resin fine particles are dispersed, and a solvent has been proposed. (See Patent Document 1). Patent Document 1 proposes the use of a resin having a cardo structure as a photopolymerizable compound because it is easy to form a cured film having excellent balance of heat resistance, mechanical properties, solvent resistance, chemical resistance, and the like. Yes.

JP 2011-170075 A

  Here, an insulating material, particularly an insulating material containing a pigment, often requires a high level of smoothness. However, when forming a cured film using a negative photosensitive resin composition as described in Patent Document 1, it may be difficult to form a smooth cured film depending on the type of solvent. Further, when the photosensitive resin composition contains a resin having a cardo structure, there is a problem that the resin having a cardo structure is likely to be precipitated.

  The present invention has been made in view of the above problems, and can provide a photosensitive resin composition capable of suppressing precipitation of a resin having a cardo structure and capable of forming a smooth cured film, and the photosensitive resin composition. It aims at providing the cured film which consists of hardened | cured material of this, and the formation method of the cured film using the said photosensitive resin composition.

  The present inventors provide a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (S) a solvent containing a resin having a cardo structure. (L) a low-boiling solvent having a boiling point under atmospheric pressure of less than 180 ° C. and (H) a high-boiling solvent having a boiling point of 180 ° C. or more and 300 ° C. or less under atmospheric pressure as the (S) solvent, respectively. It has been found that the above-mentioned problems can be solved by using a predetermined amount, and (H) a high boiling point solvent containing a compound having an aromatic hydrocarbon ring and an ester bond, and the present invention has been completed.

The first aspect of the present invention includes (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (S) a solvent.
(A) the alkali-soluble resin includes a resin having a cardo structure;
(S) the solvent includes a low boiling point solvent (L) having a boiling point of less than 180 ° C. under atmospheric pressure, and (H) a high boiling point solvent having a boiling point of 180 ° C. or more and 300 ° C. or less under atmospheric pressure;
(H) the high boiling point solvent includes a compound having an aromatic hydrocarbon ring and an ester bond,
(S) It is the photosensitive resin composition whose content of the (H) high boiling point solvent in a solvent is 1 to 30 mass%.

  A 2nd aspect of this invention is related with the cured film which consists of hardened | cured material of the photosensitive resin composition concerning a 1st aspect.

  The 3rd aspect of this invention is the photosensitive resin composition concerning a 1st aspect, Comprising: (D) The cured film which consists of hardened | cured material of the photosensitive resin composition containing a pigment.

According to a fourth aspect of the present invention, a photosensitive resin composition according to the first aspect is applied on a substrate to form a coating film;
Exposing a coating film, and forming a cured film.

  According to the present invention, it is possible to suppress the precipitation of a resin having a cardo structure and form a smooth cured film, a cured film made of a cured product of the photosensitive resin composition, and the photosensitive resin. And a method for forming a cured film using the conductive resin composition.

≪Photosensitive resin composition≫
The photosensitive resin composition contains (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (S) a solvent.
(S) The solvent includes (L) a low-boiling solvent having a boiling point of less than 180 ° C. under atmospheric pressure and (H) a high-boiling solvent having a boiling point of from 180 ° C. to 300 ° C. under atmospheric pressure.
(H) The high boiling point solvent includes a compound having an aromatic hydrocarbon ring and an ester bond.
Hereinafter, essential or optional components contained in the photosensitive resin composition will be described.

<(A) Alkali-soluble resin>
The alkali-soluble resin is a resin film having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), and a 1 μm-thick resin film is formed on the substrate and placed in a 0.05% by mass KOH aqueous solution for 1 minute. When immersed, it means a film that dissolves 0.01 μm or more in thickness.

  (A) The alkali-soluble resin essentially contains (A1) a resin having a cardo structure. (A1) By using a photosensitive resin composition containing a resin having a cardo structure as the alkali-soluble resin (A), a cured film having excellent balance of heat resistance, mechanical properties, solvent resistance, chemical resistance, etc. Easy to form.

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

In the formula ^{(a-1), X} a represents a group represented by the following formula (a-2).

In the formula (a-2), R ^a1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^a2 independently represents a hydrogen atom or a methyl group. , W ^a represents a single bond or a group represented by the following formula (a-3).

In the formula (a-1), Y ^a represents a residue obtained by removing an acid anhydride group (—CO—O—CO—) from a dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.

Further, in the above formula ^(a-1), Z a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like.
Moreover, in said formula (a-1), m shows the integer of 0-20.

  (A1) The mass average molecular weight of the resin having a cardo structure (Mw: measured value in terms of polystyrene of gel permeation chromatography (GPC). The same applies in the present specification) is preferably 1000 to 40000, and preferably 2000 to 30000. It is more preferable that By setting it as the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

  (A) The ratio of the mass of the resin having a cardo structure to the total mass of the alkali-soluble resin (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 90% by mass or more, and 100% by mass. It may be.

When the (A) alkali-soluble resin contains a resin other than the resin having the (A1) cardo structure, the other resin is not particularly limited as long as it has a predetermined alkali solubility.
Since it is easy to form a film having excellent mechanical strength and adhesion to a substrate, (A2) (a1) a copolymer obtained by polymerizing at least an unsaturated carboxylic acid is used as (A) an alkali-soluble resin. It can be suitably used together with a resin having a structure.

  (A1) Examples of unsaturated carboxylic acids 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; and anhydrides of these dicarboxylic acids; Etc. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like. These (a1) unsaturated carboxylic acids can be used alone or in combination of two or more.

  The (A2) copolymer may be a copolymer of (a1) an unsaturated carboxylic acid and (a2) an alicyclic epoxy group-containing unsaturated compound. (A2) The unsaturated compound having an alicyclic epoxy group 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 the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. These (a2) alicyclic epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

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

In the above formula, R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a22 represents a divalent having 1 to 10 carbon atoms. A hydrocarbon group is shown, t shows the integer of 0-10. R ^a21 is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^a22 , for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, —CH ₂ —Ph—CH ₂ — (Ph is A phenylene group) is preferred.

(A2) The copolymer comprises (a3) an alicyclic group-containing unsaturated compound that does not have an epoxy group, together with the (a1) unsaturated carboxylic acid and (a2) the alicyclic epoxy group-containing unsaturated compound. It may be copolymerized.
The (a3) alicyclic group-containing unsaturated compound 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 the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. These (a3) alicyclic group-containing unsaturated compounds can be used alone or in combination of two or more.

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

In the above formula, R ^a23 represents a hydrogen atom or a methyl group, R ^a24 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a25 represents a hydrogen atom or 1 carbon atom. Represents an alkyl group of ~ 5. R ^a24 is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^a25 , for example, a methyl group and an ethyl group are preferable.

  In addition, (A2) the copolymer contains a fatty acid together with the (a1) unsaturated carboxylic acid and the (a2) alicyclic epoxy group-containing unsaturated compound, and further the (a3) alicyclic group-containing unsaturated compound. (A4) An epoxy group-containing unsaturated compound having no cyclic group may be polymerized.

  (A4) Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate. (Meth) acrylic acid epoxy alkyl esters; α-ethyl glycidyl acrylate, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylate 6,7-epoxyheptyl, etc. And alkylacrylic acid epoxy alkyl esters. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate are preferable from the viewpoint of copolymerization reactivity and the strength of the cured resin. These (a4) epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

  Further, the (A2) copolymer may be obtained by further polymerizing other compounds than the above. Examples of such other compounds include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds can be used alone or in combination of two or more.

  As (meth) acrylic acid esters, linear or branched chain such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate, etc. Alkyl (meth) acrylates; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (Meth) acrylate; etc. are mentioned.

  (Meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, 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 acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Can be mentioned.

  Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl 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. Alkyl vinyl ethers such as diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichloropheny And the like; ethers, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.

  Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl vinyl. Examples include enil acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

  Styrenes include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy Alkyl styrene such as methyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl Styrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.

The proportion of the structural unit derived from the (a1) unsaturated carboxylic acid in the (A2) copolymer is preferably 1 to 50% by mass, more preferably 5 to 45% by mass.
When the copolymer (A2) contains a structural unit derived from the above (a2) alicyclic epoxy group-containing unsaturated compound and a structural unit derived from the above (a4) epoxy group-containing unsaturated compound, (A2 ) The total of the proportion of structural units derived from (a2) alicyclic epoxy group-containing unsaturated compounds in the copolymer and the proportion of structural units derived from (a4) epoxy group-containing unsaturated compounds is 71% by mass or more It is preferable that it is 71-95 mass%, it is more preferable that it is 75-90 mass%. In particular, the proportion of the structural unit derived from the (a2) alicyclic epoxy group-containing unsaturated compound in the (A2) copolymer is preferably 71% by mass or more, and preferably 71 to 80% by mass. Is more preferable. By setting the proportion of the structural unit derived from the (a2) alicyclic epoxy group-containing unsaturated compound within the above range, the temporal stability of the photosensitive resin composition can be further improved.
When the copolymer (A2) contains a structural unit derived from (a3) an alicyclic group-containing unsaturated compound, (A2) the alicyclic group-containing unsaturated compound in the copolymer (A2) The proportion of the derived structural unit is preferably 1 to 30% by mass, and 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 it as the above range, the film forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced.

  Moreover, as (A) other resins other than the resin having a cardo structure used as the alkali-soluble resin (A1), (A3) a structural unit derived from the above (a1) unsaturated carboxylic acid and (B A copolymer having at least a structural unit having a polymerizable moiety with a photopolymerizable monomer, or (A4) a structural unit derived from the (a1) unsaturated carboxylic acid and the (a2) alicyclic epoxy group. A copolymer having at least a constituent unit derived from the unsaturated compound and / or (a4) an epoxy group-containing unsaturated compound and a constituent unit having a polymerizable portion with the photopolymerizable monomer (B) described later. Resins can also be suitably used. When (A) alkali-soluble resin contains (A3) copolymer or (A4) copolymer, the adhesiveness to the board | substrate of the film | membrane formed using the photosensitive resin composition, and the photosensitive resin composition The mechanical strength of the cured film obtained using can be increased.

  (A3) Copolymer and (A4) Copolymer are described as other compounds for copolymer (A2), (meth) acrylic esters, (meth) acrylamides, allyl compounds, vinyl ethers , Vinyl esters, styrenes and the like may be further copolymerized.

  (B) The structural unit which has a site | part polymerizable with a photopolymerizable monomer has an ethylenically unsaturated group as a site | part polymerizable with (B) photopolymerizable monomer. In the copolymerization having such a constitutional unit, for (A3) the copolymer, at least a part of the carboxyl group contained in the polymer containing the constitutional unit derived from the (a1) unsaturated carboxylic acid, It can be prepared by reacting the above (a2) alicyclic epoxy group-containing unsaturated compound and / or (a4) an epoxy group-containing unsaturated compound. In addition, (A4) the copolymer is composed of (a1) a structural unit derived from an unsaturated carboxylic acid, (a2) an alicyclic epoxy group-containing unsaturated compound and / or (a4) an epoxy group-containing unsaturated compound. It can be prepared by reacting at least a part of an epoxy group in a copolymer having a derived structural unit with (a1) an unsaturated carboxylic acid.

  The proportion of the structural unit derived from the (a1) unsaturated carboxylic acid in the copolymer (A3) is preferably 1 to 50 mass%, more preferably 5 to 45 mass%. In the copolymer (A3), the proportion of the structural unit having a site polymerizable with the photopolymerizable monomer (B) is preferably 1 to 45% by mass, and more preferably 5 to 40% by mass. When a copolymer (A3) contains each structural unit in such a ratio, it is easy to obtain the photosensitive resin composition which can form the film | membrane excellent in adhesiveness with a board | substrate.

1-50 mass% is preferable and, as for the ratio for which the structural unit derived from (a1) unsaturated carboxylic acid in a copolymer (A4) accounts, 5-45 mass% is more preferable. The proportion of the structural unit derived from the (a2) alicyclic epoxy group-containing unsaturated compound and / or (a4) the epoxy group-containing unsaturated compound in the copolymer (A4) is preferably 55% by mass or more, 71 More preferably, it is more preferably 71 to 80% by mass.
In the copolymer (A4), the proportion of the structural unit having a site capable of polymerization with the photopolymerizable monomer (B) is preferably 1 to 45% by mass, and more preferably 5 to 40% by mass. When a copolymer (A4) contains each structural unit in such a ratio, it is easy to obtain the photosensitive resin composition which can form the film | membrane excellent in adhesiveness with a board | substrate.

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

  (A) The content of the alkali-soluble resin is preferably 40 to 85% by mass and more preferably 45 to 75% by mass with respect to the solid content of the photosensitive resin composition. Further, the alkali-soluble resin (A) has a total amount of 100 masses of the content of (A) the alkali-soluble tree, the content of (B) the photopolymerizable monomer, and the content of (C) the photopolymerization initiator. It is preferable to mix | blend with the photosensitive resin composition so that content of (B) photopolymerizable monomer in the photosensitive resin composition may be 5-50 mass parts.

<(B) Photopolymerizable compound>
Photopolymerizable compounds include monofunctional compounds and polyfunctional compounds.
Monofunctional compounds 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 acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- ( (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( And (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional compounds can be used alone or in combination of two or more.

  On the other hand, as polyfunctional compounds, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxy) Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly ( ) Acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene Examples thereof include polyfunctional compounds such as condensates of ether, polyhydric alcohol and N-methylol (meth) acrylamide, and triacryl formal. These polyfunctional compounds can be used alone or in combination of two or more.

  (B) It is preferable that content of a photopolymerizable compound is 1-40 mass% with respect to solid content of the photosensitive resin composition, and it is more preferable that it is 5-30 mass%. By setting it as the above range, it tends to be easy to balance sensitivity, developability, and resolution.

<(C) Photopolymerization initiator>
(C) It does not specifically limit as a photoinitiator, A conventionally well-known photoinitiator can be used.

  Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 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, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime), (9-ethyl-6-nitro-9H-carbazol-3-yl ) [4- (2-Methoxy-1-methylethoxy) -2-methylphenyl] methanone O-acetyloxime, 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Acid butyl, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamido Benzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2 -Ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzoy Dazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p ′ -Bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopro Offenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) ) Pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis ( Lichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-Dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4) -Methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2- Bromo-4-methoxy) styrylphenyl-s-triazine and the like. These photopolymerization initiators can be used alone or in combination of two or more. When two or more types are combined, it is preferable to combine an oxime photopolymerization initiator and a photopolymerization initiator other than the oxime photopolymerization initiator.

  Among these, it is particularly preferable in terms of sensitivity to use an oxime-based photopolymerization initiator. Among oxime-based photopolymerization initiators, O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl] ethanone oxime and ethanone are particularly preferable. , 1- [9-Ethyl-6- (pyrrol-2-ylcarbonyl) -9H-carbazol-3-yl], 1- (O-acetyloxime), and 1,2-octanedione, 1- [4- (Phenylthio)-, 2- (O-benzoyloxime)].

（Ｒ^ｃ１は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、
ｎ１は０〜４の整数であり、
ｎ２は０、又は１であり、
Ｒ^ｃ２は、置換基を有してもよいフェニル基、又は置換基を有してもよいカルバゾリル基であり、
Ｒ^ｃ３は、水素原子、又は炭素原子数１〜６のアルキル基である。） As the photopolymerization initiator, it is also preferable to use an oxime compound represented by the following formula (c1).

(R ^c1 is a group selected from the group consisting of a monovalent organic group, amino group, halogen, nitro group, and cyano group;
n1 is an integer of 0 to 4,
n2 is 0 or 1,
R ^c2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent,
R ^c3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )

In formula (c1), R ^c1 is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Preferable examples when R ^c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a substituent A naphthoxycarbonyl group which may have a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, Examples include an amino group substituted with an mino group, 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When n1 is an integer of 2 to 4, R ^c1 may be the same or different. Further, the number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent that the substituent further has.

When R ^c1 is an alkyl group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Further, when R ^c1 is an alkyl group, it may be linear or branched. Specific examples when R ^c1 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. When R ^c1 is an alkyl group, the alkyl group may include an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c1 is an alkoxy group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Further, when R ^c1 is an alkoxy group, it may be linear or branched. Specific examples when R ^c1 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ^c1 is an alkoxy group, the alkoxy group may include an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

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

When R ^c1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, 2 to 20 carbon atoms are preferable, and 2 to 7 carbon atoms are more preferable. Specific examples when R ^c1 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanyl group Examples include a noyl group and an n-hexadecanoyl group. Specific examples when R ^c1 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When R ^c1 is an alkoxycarbonyl group, 2 to 20 carbon atoms are preferable, and 2 to 7 carbon atoms are more preferable. Specific examples when R ^c1 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxylcarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group , Isononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group and the like.

When R ^c1 is a phenylalkyl group, 7 to 20 carbon atoms are preferable, and 7 to 10 carbon atoms are more preferable. Further, when R ^c1 is a naphthylalkyl group, the number of carbon atoms is preferably 11 to 20, and more preferably 11 to 14 carbon atoms. Specific examples when R ^c1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of when R ^c1 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2- (α-naphthyl) ethyl group, and a 2- (β-naphthyl) ethyl group. . When R ^c1 is a phenylalkyl group or a naphthylalkyl group, R ^c1 may further have a substituent on the phenyl group or naphthyl group.

When R ^c1 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing 1 or more of N, S, and O, or such monocycles or such monocycles and a benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline. When R ^c1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c1 is an amino group substituted with an organic group of 1 or 2, suitable examples of the organic group include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, carbon A saturated aliphatic acyl group having 2 to 20 atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenyl having 7 to 20 carbon atoms which may have a substituent Examples thereof include an alkyl group, an optionally substituted naphthyl group, an optionally substituted naphthoyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, and a heterocyclyl group. It is done. Specific examples of these suitable organic groups are the same as those for R ^c1 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

In the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c1 further have a substituent, the substituent is as follows: an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carbon atom A monoalkylamino group having a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms And 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, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c1 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c1 have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^c1 , since it is chemically stable, has few steric hindrances, and is easy to synthesize an oxime ester compound, an alkyl group having 1 to 6 carbon atoms, 1 to 1 carbon atoms, and the like. A group selected from the group consisting of 6 alkoxy groups and saturated aliphatic acyl groups having 2 to 7 carbon atoms is preferred, alkyls having 1 to 6 carbon atoms are more preferred, and methyl groups are particularly preferred.

Position R ^c1 is bonded to the phenyl group, the phenyl group R ^c1 are attached the position of the bond to the main chain of the phenyl group and the oxime ester compound as a 1-position, if the 2-position of the position of the methyl group 4th or 5th is preferable, and 5th is more preferable. N1 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

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

In R ^c2 , the substituent that the phenyl group or carbazolyl group has is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that the phenyl group or carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 3 carbon atoms. -10 cycloalkyl group, C3-C10 cycloalkoxy group, C2-C20 saturated aliphatic acyl group, C2-C20 alkoxycarbonyl group, C2-C20 saturated Aliphatic acyloxy group, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted phenylthio group, optionally substituted benzoyl group, substituted A phenoxycarbonyl group which may have a group, a benzoyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, and a substituent. Naphthyl A naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a substituent A naphthylalkyl group having 11 to 20 carbon atoms which may have a group, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, 1 or 2 organic groups Examples include an amino group substituted with a group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group.

When R ^c2 is a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include alkyl groups having 1 to 20 carbon atoms and cycloalkyl groups 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, and a substituent. A phenoxycarbonyl group which may have, 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 naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent; Heterogeneity And a krylcarbonyl group. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent that the phenyl group or carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. With respect to an optionally substituted phenylalkyl group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, and an amino group substituted with one or two organic groups , R ^c1 .

Examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent that the phenyl group or the carbazolyl group has in R ^c2 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; Benzoyl group; benzoyl group; benzoyl substituted by a group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, and 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; Examples include a holin-1-yl group; a piperazin-1-yl group; a halogen; a nitro group; and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent of the phenyl group or carbazolyl group further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. 1-4 are preferable. When the phenyl group, naphthyl group, and heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

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

（Ｒ^ｃ４は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、ＡはＳ又はＯであり、ｎ３は、０〜４の整数である。）

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

（Ｒ^ｃ５及びＲ^ｃ６は、それぞれ、１価の有機基である。）

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

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

In ^Rc4 , substituted with a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group Benzoyl group; nitro group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferred.

In formula (c2), n3 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. If n3 is 1, binding position of R ^c4, to the bond to the phenyl group R ^c4 is bonded is bonded to an oxygen atom or a sulfur atom, it is preferably in the para position.

R ^c5 in formula (c3) can be selected from various organic groups as long as the object of the present invention is not ^impaired . Preferable examples of R ^c5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, and 2 to 20 carbon atoms. Alkoxycarbonyl group, phenyl group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, carbon atoms which may have a substituent 7 ~ 20 phenylalkyl group, optionally substituted naphthyl group, optionally substituted naphthoyl group, optionally substituted naphthoxycarbonyl group, optionally substituted Examples thereof include a naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

Among R ^c5 , 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 ^c6 in formula (c3) is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Specific examples of the group suitable as R ^c6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. The heterocyclyl group which may be sufficient is mentioned. Among these groups, R ^c6 is more preferably a phenyl group which may have a substituent, and particularly preferably a 2-methylphenyl group.

^Examples of the substituent when the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 further have a substituent include an alkyl group having 1 to 6 carbon atoms, and 1 to 1 carbon atom. 6 alkoxy groups, saturated aliphatic acyl groups having 2 to 7 carbon atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms, saturated aliphatic acyloxy groups having 2 to 7 carbon atoms, alkyl having 1 to 6 carbon atoms And a monoalkylamino group having a group, 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, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, 1-4 are preferable. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 have a plurality of substituents, the plurality of substituents may be the same or different.

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

When p is 0, the oxime ester compound represented by the formula (c1) can be synthesized according to the following scheme 1, for example. Specifically, an aromatic compound represented by the following formula (c1-1) is acylated by a Friedel-Crafts reaction using a halocarbonyl compound represented by the following formula (c1-2), and the following formula: A ketone compound represented by (c1-3) is obtained, and the resulting ketone compound (c1-3) is oximed with hydroxylamine to obtain an oxime compound represented by the following formula (c1-4), and then the formula The hydroxy group in the oxime compound of (c1-4) can be acylated to obtain an oxime ester compound represented by the following formula (c1-7). As an acylating agent, an acid anhydride (R ^c3 COHal, Hal represented by the following formula (c 1-6) or an acid anhydride ((R ^c3 CO) ₂ O) represented by the following formula (c 1-5) Is preferably halogen.). In the following formula (c1-2), Hal is halogen, and in the following formulas (c1-1), (c1-2), (c1-3), (c1-4), and (c1-7) , R ^c1 , R ^c2 , R ^c3 , and n1 are the same as those in the formula (c1).

<Scheme 1>

When n2 is 1, the oxime ester compound represented by the formula (c1) can be synthesized according to the following scheme 2, for example. Specifically, a ketone compound represented by the following formula (c2-1) is added to a nitrite ester (RONO, R is represented by 1 to 6 carbon atoms) represented by the following formula (c2-2) in the presence of hydrochloric acid. To obtain a ketoxime compound represented by the following formula (c2-3), and then acylate the hydroxy group in the ketoxime compound represented by the following formula (c2-3). An oxime ester compound represented by the following formula (c2-6) can be obtained. As an acylating agent, an acid anhydride (R ^c3 COHal, Hal represented by the following formula ( ^c 2-5) or an acid anhydride (R ^c3 CO) ₂ O represented by the following formula (c2-4) Is preferably halogen.). In the following formulas (c2-1), (c2-3), (c2-4), (c2-5), and (c2-6), R ^c1 , R ^c2 , R ^c3 , and n1 are formulas Same as (c1).

<Scheme 2>

Further, the oxime ester compound represented by the formula (c1) is, n2 is ^1, and ^{R c1} is a methyl ^group, with respect to methyl groups attached to the benzene ring ^{to which R c1} are ^{attached, R c1} para In the case of bonding to a position, for example, a compound represented by the following formula (c2-7) can be synthesized by oximation and acylation in the same manner as in Scheme 1. In the following formula (c2-7), R ^c2 is the same as in formula (c1).

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

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

（Ｒ^ｃ７は水素原子、ニトロ基又は１価の有機基であり、Ｒ^ｃ８及びＲ^ｃ９は、それぞれ、置換基を有してもよい鎖状アルキル基、置換基を有してもよい環状有機基、又は水素原子であり、Ｒ^ｃ８とＲ^ｃ９とは相互に結合して環を形成してもよく、Ｒ^ｃ１０は１価の有機基であり、Ｒ^ｃ１１は、水素原子、置換基を有してもよい炭素原子数１〜１１のアルキル基、又は置換基を有してもよいアリール基であり、ｎ４は０〜４の整数であり、ｎ５は０又は１である。）

(R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group, and R ^c8 and R ^c9 are each a chain alkyl group which may have a substituent, or a cyclic organic which may have a substituent. R ^c8 and R ^c9 may be bonded to each other to form a ring, R ^c10 is a monovalent organic group, and R ^c11 has a hydrogen atom or a substituent. An alkyl group having 1 to 11 carbon atoms, or an aryl group which may have a substituent, n4 is an integer of 0 to 4, and n5 is 0 or 1.)

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

（Ｒ^ｃ７、Ｒ^ｃ８、Ｒ^ｃ９、Ｒ^ｃ１０、ｎ４、及びｎ５は、式（ｃ４）と同様である。）

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

In formulas (c4) and (c5), R ^c7 is a hydrogen atom, a nitro group, or a monovalent organic group. R ^c7 is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by — (CO) _n5 — on the fluorene ring in the formula (c4). In formula (c4), the bonding position of R ^{c7 to} the fluorene ring is not particularly limited. When the compound represented by the formula (c4) has one or more R ^c7 , one of the one or more R ^c7 is a fluorene ring because synthesis of the compound represented by the formula (c4) is easy. Bonding at the 2-position is preferable. If R ^c7 is more, a plurality of R ^c7 is independently in may be the same or different.

When R ^c7 is an organic group, R ^c7 is not particularly limited as long as the object of the present invention is not ^{impaired, and} is appropriately selected from various organic groups. Preferred examples of when R ^c7 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a substituent An optionally substituted naphthoxycarbonyl group, an optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, Examples include a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

When R ^c7 is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1-20, and more preferably 1-6. Further, when R ^c7 is an alkyl group, it may be linear or branched. Specific examples when R ^c7 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. When R ^c7 is an alkyl group, the alkyl group may include an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c7 is an alkoxy group, the alkoxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms. Further, when R ^c7 is an alkoxy group, it may be linear or branched. Specific examples when R ^c7 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ^c7 is an alkoxy group, the alkoxy group may include an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

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

When R ^c7 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, and more preferably 2 to 7. Specific examples when R ^c7 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanyl group Examples include a noyl group and an n-hexadecanoyl group. Specific examples when R ^c7 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When R ^c7 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, and more preferably 2-7. Specific examples when R ^c7 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, Examples include an isononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

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

When R ^c7 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing 1 or more of N, S, and O, or such monocycles or such monocycles and a benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. It is done. When R ^c7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

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

When R ^c7 is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, and carbon atoms. A saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl having 7 to 20 carbon atoms which may have a substituent Group, an optionally substituted naphthyl group, an optionally substituted naphthoyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, and a heterocyclyl group. . Specific examples of these suitable organic groups are the same as those for R ^c7 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

In the case where the phenyl group, the naphthyl group, and the heterocyclyl group included in R ^c7 further have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom. A monoalkylamino group having a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms And 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, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c7 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c7 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, R ^c7 is preferably a nitro group or a group represented by R ^c12 —CO— because the sensitivity tends to be improved. R ^c12 is not particularly limited as long as the object of the present invention is not ^impaired , and can be selected from various organic groups. Examples of groups suitable as R ^c12 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Or a heterocyclyl group that may be used. As R ^c12 , among these groups, a 2-methylphenyl group, a thiophen-2-yl group, and an α-naphthyl group are particularly preferable.
Moreover, it is preferable that R ^c7 is a hydrogen atom because transparency tends to be good. When R ^c7 is a hydrogen atom and R ^c10 is a group represented by the following formula (c4b), the transparency tends to be better.

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

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

When R ^c8 and R ^c9 are chain alkyl groups having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear.
The substituent that the alkyl group may have is not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as the preferred examples in the case where R ^c7 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group. Specific examples of the heterocyclyl group are the same as the preferred examples when R ^c7 is a heterocyclyl group. When R ^c7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. 1-10 are preferable and, as for the carbon atom number of the alkoxy group contained in an alkoxycarbonyl group, 1-6 are more preferable.

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

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

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

When R ^c8 and R ^c9 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. Although the carbon atom number of an aliphatic cyclic hydrocarbon group is not specifically limited, 3-20 are preferable and 3-10 are more preferable. Examples of monocyclic cyclic hydrocarbon groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, Examples include a tetracyclododecyl group and an adamantyl group.

When R ^c8 and R ^c9 are heterocyclyl groups, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, O, such monocycles, or such monocycles and a benzene ring. And a condensed heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. It is done.

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

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

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

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

Preferable specific examples of R ^c8 and R ^c9 include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl Group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -N-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n − Cyanoalkyl groups such as an nyl group, a 6-cyano-n-hexyl group, a 7-cyano-n-heptyl group, and an 8-cyano-n-octyl group; a 2-phenylethyl group, a 3-phenyl-n-propyl group Phenylalkyl such as 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and 8-phenyl-n-octyl group Groups: 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n- Heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopent Cycloalkylalkyl groups such as ru-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxy Carbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n -Pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxy Alkoxycarbonylalkyl groups such as rubonyl-n-heptyl and 8-ethoxycarbonyl-n-octyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro -N-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo -N-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoro Examples thereof include a propyl group and a halogenated alkyl group such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

Among R ^c8 and R ^c9 , preferred groups among the above are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-hepta A fluoro-n-pentyl group;

Examples of suitable organic groups for R ^c10 are the same as for R ^c7 , alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, substituents. 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, and a substituent A good benzoyloxy group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, A naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocycle which may have a substituent Group, an optionally substituted heterocyclyl group, 1, or an amino group substituted with two organic groups, morpholin-1-yl group, and piperazine-1-yl group. Specific examples of these groups are the same as those described for R ^c7 . R ^c10 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The substituent that the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent that the phenyl group contained in R ^c7 may have.

Among organic groups, as R ^c10 , an alkyl group, a cycloalkyl group, an ^optionally substituted phenyl group, or a cycloalkylalkyl group, or an optionally substituted phenylthio group on an aromatic ring. Alkyl groups are preferred. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. Among the phenyl groups that may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. 1-8 are preferable, as for the carbon atom number of the alkylene group contained in a cycloalkylalkyl group, 1-4 are more preferable, and 2 is especially preferable. Of the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. 1-8 are preferable, as for the carbon atom number of the alkylene group contained in the phenylthioalkyl group which may have a substituent on an aromatic ring, 1-4 are more preferable, and 2 is especially preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2- (4-chlorophenylthio) ethyl group is preferable.

In addition, as R ^c10 , a group represented by —A ³ —CO—O—A ⁴ is also preferable. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ⁴ is a monovalent organic group, and is preferably a monovalent hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. If A ³ is an alkylene group, number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, 1 to 4 are particularly preferred.

Preferable examples of A ⁴ include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Preferred examples of A ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl. Group, phenyl group, naphthyl group, benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group and the like.

Preferred examples of the group represented by —A ³ —CO—O—A ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n -Butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl Group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl -n- propyl group, and 3-phenoxycarbonyl -n- propyl group and the like.

（式（ｃ４ａ）及び（ｃ４ｂ）中、Ｒ^ｃ１３及びＲ^ｃ１４はそれぞれ有機基であり、ｎ６は０〜４の整数であり、Ｒ^ｃ１３及びＲ^ｃ１４がベンゼン環上の隣接する位置に存在する場合、Ｒ^ｃ１３とＲ^ｃ１４とが互いに結合して環を形成してもよく、ｎ７は１〜８の整数であり、ｎ８は１〜５の整数であり、ｎ９は０〜（ｎ８＋３）の整数であり、Ｒ^ｃ１５は有機基である。） ^Having described ^{R c10,} as the ^{R c10,} preferably a group represented by the following formula (C4a) or (C4b).

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

Examples of the organic group for R ^c13 and R ^{c14 in} formula (c4a) are the same as those for R ^c7 . R ^c13 is preferably an alkyl group or a phenyl group. When R ^c13 is an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R ^c13 is most preferably a methyl group. When R ^c13 and R ^c14 combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferred examples of the group represented by the formula (c4a) in which R ^c13 and R ^c14 form a ring include a naphthalen-1-yl group, 1,2,3,4- And tetrahydronaphthalen-5-yl group. In said formula (c4a), n6 is an integer of 0-4, It is preferable that it is 0 or 1, and it is more preferable that it is 0.

In the above formula (c4b), R ^c15 is an organic group. ^Examples of the organic group include the same groups as those described for R ^c7 . Of the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. 1-10 are preferable, as for the carbon atom number of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. As R ^c15 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

  In said formula (c4b), n8 is an integer of 1-5, the integer of 1-3 is preferable and 1 or 2 is more preferable. In said formula (c4b), n9 is 0- (n8 + 3), the integer of 0-3 is preferable, the integer of 0-2 is more preferable, and 0 is especially preferable. In said formula (c4b), n7 is an integer of 1-8, the integer of 1-5 is preferable, the integer of 1-3 is more preferable, and 1 or 2 is especially preferable.

In formula (c4), R ^c11 represents a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. Preferred examples of the substituent that may be present when R ^c11 is an alkyl group include a phenyl group and a naphthyl group. In addition, preferred examples of the substituent that may be present when R ^c7 is an aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

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

The compound represented by the formula (c4) represents an oxime group (> C═N—OH) contained in the compound represented by the above formula (c5) by> C═N—O—COR ^c11. It is produced by a method including a step of converting to an oxime ester group. R ^c11 are the same as ^{R c11} in formula (c4).

The conversion of the oxime group (> C═N—OH) to the oxime ester group represented by> C═N—O—COR ^c11 involves conversion of the compound represented by the above formula (c5), an acylating agent, It is performed by reacting.
The acylating agent to give the acyl group represented by -COR ^{c11, (R c11} _CO) or an acid anhydride represented by ₂ ^O, R c11 COHal (Hal is a halogen atom) include acid halide represented by It is done.

When n5 is 0, the compound represented by the general formula (c4) can be synthesized according to the following scheme 3, for example. In Scheme 3, a fluorene derivative represented by the following formula (c3-1) is used as a raw material. When R ^c7 is a nitro group or a monovalent organic group, the fluorene derivative represented by the formula (c3-1) is converted into a fluorene derivative substituted at the 9-position with R ^c8 and R ^c9 by a known method. It can be obtained by introducing the substituent R ^c7 . The fluorene derivative substituted at the 9-position with R ^c8 and R ^c9 is, for example, an alkali metal hydroxide as described in JP-A No. 06-234668 when R ^c8 and R ^c9 are alkyl groups. It can be obtained by reacting fluorene with an alkylating agent in the presence of an aprotic polar organic solvent. In addition, an alkylating agent such as an alkyl halide, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide are added to an organic solvent solution of fluorene. By performing the alkylation reaction, 9,9-alkyl-substituted fluorene can be obtained.

An acyl group represented by —CO—R ^c10 is introduced into the fluorene derivative represented by the formula (c3-1) by Friedel-Crafts acylation reaction, and the fluorene derivative represented by the formula (c3-3) can get. The acylating agent for introducing an acyl group represented by —CO—R ^c10 may be a halocarbonyl compound or an acid anhydride. As the acylating agent, a halocarbonyl compound represented by the formula (c3-2) is preferable. In formula (c3-2), Hal is a halogen atom. The position at which the acyl group is introduced on the fluorene ring can be selected by changing the Friedel-Crafts reaction conditions as appropriate, or by performing protection and deprotection at other positions where acylation is performed. it can.

Next, the group represented by —CO—R ^c10 in the fluorene derivative represented by the formula (c3-3) to be obtained is converted into a group represented by —C (═N—OH) —R ^c10 , An oxime compound represented by the formula (c3-4) is obtained. The method for converting the group represented by —CO—R ^c10 to the group represented by —C (═N—OH) —R ^c10 is not particularly limited, but oximation with hydroxylamine is preferred. An oxime compound of the formula (c3-4) and an acid anhydride ((R ^c11 CO) ₂ O) represented by the following formula (c3-5) or an acid halide represented by the following formula (c3-6) ( R ^c11 COHal, Hal is a halogen atom) and a compound represented by the following formula (c3-7) can be obtained.

In the formulas (c3-1), (c3-2), (c3-3), (c3-4), (c3-5), (c3-6), and (c3-7), R ^c7 , R ^c8 , R ^c9 , R ^c10 , and R ^c11 are the same as those in formula (c4).

In Scheme 3, R ^c10 contained in each of formula (c3-2), formula (c3-3), and formula (c3-4) may be the same or different. That is, R ^c10 in formula (c3-2), formula (c3-3), and formula (c3-4) may undergo chemical modification in the synthesis process shown as Scheme 3. Examples of chemical modification include esterification, etherification, acylation, amidation, halogenation, substitution of a hydrogen atom in an amino group with an organic group, and the like. The chemical modification that R ^c10 may undergo is not limited thereto.

<Scheme 3>

When n5 is 1, the compound represented by the formula (c4) can be synthesized according to the following scheme 4, for example. In Scheme 4, a fluorene derivative represented by the following formula (c4-1) is used as a raw material. The fluorene derivative represented by the formula (c4-1) is represented by —CO—CH ₂ —R ^c10 by a Friedel-Crafts reaction to a compound represented by the formula (c3-1) by the same method as in Scheme 3. It is obtained by introducing an acyl group. The acylating agent of the formula (C3-8): carboxylic acid halide is preferably represented by ^{_{Hal-CO-CH 2 -R c10}} . Subsequently, the methylene group present between R ^c10 and the carbonyl group in the compound represented by the formula (c4-1) is oximed to obtain a ketoxime compound represented by the following formula (c4-3). The method for oximation of the methylene group is not particularly limited, but a nitrite represented by the following formula (c4-2) (RONO, R is an alkyl group having 1 to 6 carbon atoms) is reacted in the presence of hydrochloric acid. The method of making it preferable is. Next, a ketoxime compound represented by the following formula (c4-3) and an acid anhydride ((R ^c11 CO) ₂ O) represented by the following formula (c4-4) or the following formula (c4-5) A compound represented by the following formula (c4-6) can be obtained by reacting with an acid halide (R ^c11 COHal, Hal is a halogen atom). In the following formulas (c4-1), (c4-3), (c4-4), (c4-5), and (c4-6), R ^c7 , R ^c8 , R ^c9 , R ^c10 , and R ^c11 is the same as that of Formula (c4).
When n5 is 1, there exists a tendency which can reduce more the generation | occurrence | production of the foreign material in the pattern formed using the photosensitive resin composition containing the compound represented by Formula (c4).

In scheme 4, R ^c10 contained in each of formula (c3-8), formula (c4-1), and formula (c4-3) may be the same or different. That is, R ^c10 in formula (c3-8), formula (c4-1), and formula (c4-3) may undergo chemical modification in the synthesis process shown as Scheme 4. Examples of chemical modification include esterification, etherification, acylation, amidation, halogenation, substitution of a hydrogen atom in an amino group with an organic group, and the like. The chemical modification that R ^c10 may undergo is not limited thereto.

<Scheme 4>

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

  (C) It is preferable that content of a photoinitiator is 0.5-20 mass parts with respect to 100 mass parts of solid content of the photosensitive resin composition. By setting it as said range, it is easy to prepare the photosensitive resin composition which has favorable applicability | paintability and sclerosis | hardenability.

<(D) Pigment>
As the photosensitive resin composition, those containing no (D) pigment are preferred, and those containing (D) a pigment are also preferred. (D) Since the photosensitive resin composition which does not contain a pigment can form a transparent cured film, for example, it is useful in the formation of a transparent insulating film, for example. The photosensitive resin composition containing (D) pigment can form cured films colored in various hues according to the hue of (D) pigment, and is useful in the formation of color filters and black column spacers.

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

  Examples of the pigment (D) include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index: (C.I.) It is preferable to use what is numbered.

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

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

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

  Examples of red pigments that can be suitably used include C.I. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same, and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57: 1, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 1 8, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

  Examples of blue pigments that can be suitably used include C.I. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same, and only the number is described) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 , And 66.

  Examples of pigments of other hues that can be suitably used include C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment Green 37 and other green pigments, C.I. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigments such as CI Pigment Brown 28, C.I. I. Pigment black 1, C.I. I. And black pigments such as CI Pigment Black 7.

  The pigment (D) is also preferably a light shielding agent. (D) By using a photosensitive resin composition containing a light-shielding agent as a pigment, a black column spacer, a black matrix, or the like having suitable characteristics can be formed. (D) When using a pigment as a light shielding agent, it is preferable to use a black pigment or a purple pigment as the light shielding agent. Examples of black pigments and purple pigments include carbon black, perylene pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxides, metal sulfides In addition, various pigments can be mentioned regardless of organic matter or inorganic matter such as metal sulfate or metal carbonate. Among these, it is preferable to use carbon black having high light shielding properties.

  As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used, but it is preferable to use channel black having excellent light shielding properties. Resin-coated carbon black may also be used.

  As the carbon black, carbon black subjected to a treatment for introducing an acidic group is also preferable. The acidic group introduced into carbon black is a functional group that exhibits acidity according to the Bronsted definition. Specific examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The acidic group introduced into the carbon black may form a salt. The cation that forms a salt with the acidic group is not particularly limited as long as the object of the present invention is not impaired. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions, and the like, and alkali metal ions such as sodium ion, potassium ion, lithium ion, and ammonium ion are preferable.

  Among the carbon blacks that have been treated to introduce acidic groups as described above, the light-blocking cured film formed using the photosensitive resin composition has a low relative dielectric constant, and thus has a carboxylic acid group and a carboxylic acid group. Carbon black having one or more functional groups selected from the group consisting of a base, a sulfonic acid group, and a sulfonic acid group is 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 of diazo coupling an organic compound having an amino group and an acidic group with carbon black.
3) A method of reacting an organic compound having a halogen atom and an acidic group with carbon black having a hydroxyl group by Williamson's etherification method.
4) A method of reacting an organic compound having a halocarbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group.
5) A method of performing deprotection after performing a Friedel-Crafts reaction on carbon black using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group.

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

  The number of moles of acidic groups introduced into carbon black is not particularly limited as long as the object of the present invention is not impaired. 1-200 mmol is preferable with respect to 100 g of carbon black, and, as for the number of moles of the acidic group introduce | transduced into carbon black, 5-100 mmol is more preferable.

Carbon black introduced with acidic groups may be coated with a resin.
When a photosensitive resin composition containing carbon black coated with a resin is used, it is easy to form a light-shielding cured film having excellent light-shielding properties and insulating properties and low surface reflectance. In addition, the bad influence with respect to the dielectric constant of the light-shielding cured film formed using a photosensitive resin composition does not produce especially by the coating process by resin. Examples of resins that can be used to coat carbon black include thermosetting resins such as phenolic resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, poly Examples thereof include thermoplastic resins such as butylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, and polyether ether ketone. The coating amount of the resin on the carbon black is preferably 1 to 30% by mass with respect to the total of the mass of the carbon black and the mass of the resin.

  A perylene pigment is also preferable as the light-shielding agent. Specific examples of the perylene pigment include the perylene pigment represented by the following formula (d-1), the perylene pigment represented by the following formula (d-2), and the following formula (d-3). Perylene pigments. As commercial products, product names K0084 and K0086 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, 34, and the like can be preferably used as perylene pigments.

式（ｄ−１）中、Ｒ^ｄ１及びＲ^ｄ２は、それぞれ独立に炭素原子数１〜３のアルキレン基を表し、Ｒ^ｄ３及びＲ^ｄ４は、それぞれ独立に、水素原子、水酸基、メトキシ基、又はアセチル基を表す。

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

式（ｄ−２）中、Ｒ^ｄ５及びＲ^ｄ６は、それぞれ独立に、炭素原子数１〜７のアルキレン基を表す。

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

式（ｄ−３）中、Ｒ^ｄ７及びＲ^ｄ８は、それぞれ独立に、水素原子、炭素原子数１〜２２のアルキル基であり、Ｎ，Ｏ、Ｓ、又はＰのヘテロ原子を含んでいてもよい。Ｒ^ｄ７及びＲ^ｄ８がアルキル基である場合、当該アルキル基は、直鎖状であっても、分岐鎖状であってもよい。

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

  Examples of the compound represented by the formula (d-1), the compound represented by the formula (d-2), and the compound represented by the formula (d-3) include, for example, JP-A-62-17353. Can be synthesized using the method described in JP-B 63-26784. That is, perylene-3,5,9,10-tetracarboxylic acid or a dianhydride thereof and an amine are used as raw materials, and a heating reaction is performed in water or an organic solvent. The target product can be obtained by reprecipitation of the obtained crude product in sulfuric acid or recrystallization in water, an organic solvent or a mixed solvent thereof.

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

  The light-shielding agent may contain a dye having a hue such as red, blue, green, and yellow together with the black pigment and the purple pigment for the purpose of adjusting the color tone. The pigment of other hues of the black pigment and the purple pigment can be appropriately selected from known pigments. For example, the above-mentioned various pigments can be used as the coloring matter of other hues of black pigments and purple pigments. The amount of the dye having a hue other than the black pigment or the purple pigment is preferably 15% by mass or less and more preferably 10% by mass or less with respect to the total mass of the light shielding agent.

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

  In addition, the inorganic pigment and the organic pigment may be used alone or in combination of two or more, but when used in combination, the organic pigment is added in an amount of 10 to 80% by mass with respect to the total mass of the inorganic pigment and the organic pigment. It is preferably used in the range, and more preferably in the range of 20 to 40% by mass.

  The amount of the (D) pigment used in the photosensitive resin composition can be appropriately selected within a range that does not impair the object of the present invention, and is typically 5 to 5% by mass relative to the solid content in the photosensitive resin composition. 70 mass% is preferable and 25-60 mass% is more preferable.

  (D) It is preferable to add the pigment to the photosensitive resin composition after preparing a dispersion in which the pigment is dispersed at an appropriate concentration using a dispersant.

In the conventional photosensitive resin composition, when the (D) pigment is used as the colorant, depending on the type of the (S) solvent, the aggregation of the pigment particles may occur or the viscosity of the photosensitive resin composition may increase. There is a case.
However, when the photosensitive resin composition contains a compound containing an aromatic hydrocarbon ring and an ester bond described later as the (S) solvent, thickening during storage of the photosensitive resin composition or aggregation of pigment particles Can be suppressed.

<(S) Solvent>
The photosensitive resin composition contains (S) a solvent. (S) The solvent contains a combination of (L) a low-boiling solvent having a boiling point of less than 180 ° C. under atmospheric pressure and (H) a high-boiling solvent having a boiling point of from 180 ° C. to 300 ° C. under atmospheric pressure. .
Hereinafter, (L) the low boiling point solvent and (H) the high boiling point solvent will be described.

((L) Low boiling point solvent)
The (S) solvent includes (L) a low-boiling solvent having a boiling point of less than 180 ° C. under atmospheric pressure.
When a predetermined amount (S) of the (L) low-boiling solvent having a boiling point within such a range is contained in the solvent, the photosensitive resin composition is applied to the substrate to form a coating film. The (S) solvent volatilizes at a speed, and the remaining amount of the (S) solvent in the coating film can be reduced.
(L) The boiling point of the low boiling point solvent under atmospheric pressure is not particularly limited as long as it is less than 180 ° C, but it is preferably 100 ° C or more and less than 180 ° C.

  (L) Specific examples of the low boiling point solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether. , Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, tetrahydrofuran, methyl ethyl ketone, 2-heptanone, 3-heptanone, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, formic acid n -Pentyl, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopybutyrate Pill, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, N, N-dimethylformamide, N, N-dimethylacetamide, N, N, N ′, N′-tetramethylurea, propylene Examples include glycol monomethyl ether acetate, dipropylene glycol dimethyl ether, cyclohexanone, 3-methoxybutanol, 3-methoxybutyl acetate, cyclohexanol acetate, and cyclopentanone.

  From the viewpoint of odor, the (S) solvent is an alicyclic solvent such as cyclohexanone and cyclohexanol acetate, a chain aliphatic ketone solvent having 6 or more carbon atoms such as 2-heptanone and 3-heptanone, and anisole. It is preferable that the solvent is not contained.

Among the above (L) low-boiling solvents, propylene glycol monomethyl is preferable because it can easily dissolve the components blended in the photosensitive resin composition and it is easy to prepare a photosensitive resin composition with good coatability. Ether acetate, 3-methoxybutyl acetate, and 3-methoxybutanol are preferred. The (S) solvent may contain a combination of two or more of these (L) low-boiling solvents.
From the point that the components of the photosensitive resin composition can be dissolved well and the photosensitive resin composition having an appropriate drying property can be easily obtained, the combination of (L) low boiling point solvent is propylene glycol monomethyl ether. A combination of acetate and 3-methoxybutyl acetate is preferred.
Further, from the viewpoint of high-speed coating, the viscosity of the (L) low boiling point solvent is preferably less than 2 cP (2 mPa · s).

((H) high boiling point solvent)
(H) The high boiling point solvent is an organic solvent having a boiling point of 180 ° C. or higher and 300 ° C. or lower under atmospheric pressure. (H) The high boiling point solvent contains a compound containing an aromatic hydrocarbon ring and an ester bond.
(H) The boiling point of the high-boiling solvent under atmospheric pressure is preferably 180 ° C. or higher and 250 ° C. or lower, since the residual amount of the (H) high-boiling solvent in the coating film or cured film tends to be low. 220 degrees C or less is more preferable.
(H) The high boiling point solvent has a boiling point within such a range and contains a compound having the above specific structure, thereby suppressing precipitation of a resin having a cardo structure and forming a smooth cured film. It can be compatible.

  When the photosensitive resin composition contains a high-boiling organic solvent (H) having a boiling point of 180 ° C. or higher and 300 ° C. or lower, when the coating film made of the photosensitive resin composition is dried, rapid drying, The bumping of the solvent is suppressed. For this reason, it is easy to form a smooth coating film, and as a result, it is easy to form a smooth cured film.

Moreover, the photosensitive resin composition contains the resin which has a cardo structure as (A) alkali-soluble resin. However, the resin having a cardo structure may be hardly soluble depending on the type of the (S) solvent. For this reason, the resin having a cardo structure often precipitates in the conventional photosensitive resin composition.
However, when the photosensitive resin composition contains a compound having an aromatic hydrocarbon group and an ester bond, the resin having a cardo structure can be stably dissolved in the (S) solvent.

Furthermore, in the (S) solvent used for the photosensitive resin composition, the above-described alicyclic solvents such as cyclohexanone and cyclohexanol acetate, chains having 6 or more carbon atoms such as 2-heptanone and 3-heptanone. Some of them have problems in terms of odor such as a solvent such as an aliphatic ketone solvent and anisole.
On the other hand, a compound having an aromatic hydrocarbon ring and an ester bond does not generate an unpleasant odor. Thus, a compound having an aromatic hydrocarbon ring and an ester bond is a preferable (S) solvent from the viewpoint of odor.

  The (H) high boiling point solvent may be a compound that is homogenized with the (L) low boiling point solvent in the photosensitive resin composition. For this reason, the (H) high boiling point solvent may be solid under the temperature conditions in which the photosensitive resin composition is used.

(H) Among compounds having an aromatic hydrocarbon ring and an ester bond used as a high-boiling solvent, an aliphatic carboxylic acid has a low boiling point because it easily dissolves a resin having a cardo structure. One or more selected from the group consisting of benzyl esters of acids and alkyl esters of benzoic acid are preferred.
The number of carbon atoms in the benzyl ester of aliphatic carboxylic acid and the alkyl ester of benzoic acid is not limited as long as the boiling point of these compounds at atmospheric pressure is in the range of 180 ° C. or higher and 300 ° C. or lower.

Preferred examples of the compound having an aromatic hydrocarbon ring and an ester bond include methyl benzoate (about 200 ° C.), ethyl benzoate (about 212 ° C.), n-propyl benzoate (about 230 ° C.), and Alkyl esters of benzoic acid such as n-butyl benzoate (about 250 ° C.); 2-hydroxyethyl benzoate (about 289 ° C.), 2-methoxyethyl benzoate (about 225 ° C.), and 2-ethoxyethyl benzoate ( Alkoxyalkyl esters of benzoic acid such as about 244 ° C .; naphthoic acid esters such as methyl 2-naphthoate (about 290 ° C.); phenyl acetate (about 195 ° C.), p-tolyl acetate (about 210 ° C.), acetic acid m -Tolyl (about 210 ° C), o-tolyl acetate (about 208 ° C), p-methoxyphenyl acetate (about 246 ° C), m-methoxyphenyl acetate (about 250 ° C), and Acetic acid aryl esters such as o-methoxyphenyl acetate (about 240 ° C.); Propionic acid aryl esters such as phenyl propionate (about 211 ° C.) and p-tolyl propionate (about 232 ° C.); Methyl phenyl acetate (about 216 ° C), phenyl acetates such as ethyl phenylacetate (about 226 ° C), and n-propyl phenylacetate (about 244 ° C); methyl 3-phenylpropionate (about 238 ° C), and ethyl 3-phenylpropionate 3-phenylpropionic acid esters such as (about 248 ° C); phenoxyacetic acid esters such as methyl phenoxyacetate (about 244 ° C) and ethyl phenoxyacetate (about 248 ° C); benzyl acetate (about 212 ° C), propionic acid Benzyl (about 222 ° C), benzyl butanoate (about 240 ° C), and pentanoic acid Benzyl esters of aliphatic carboxylic acids such as benzyl (about 260 ° C.); phenethyl acetate (about 238 ° C.), phenethyl propionate (244 ° C.), phenethyl butanoate (about 270 ° C.), and phenethyl pentanoate (about 288 ° C.) Phenethyl esters of aliphatic carboxylic acids such as: methyl p-hydroxybenzoate (about 280 ° C.), ethyl p-chlorobenzoate (about 238 ° C.), methyl p-anisate (about 244 ° C.), and o-anisic acid Alkyl esters of substituted benzoic acids such as methyl (about 248 ° C.); alkyl esters of cinnamic acid such as methyl cinnamate (about 262 ° C.) and ethyl cinnamate (about 271 ° C.); dimethyl phthalate (about 283 ° C.), And dialkyl esters of benzenedicarboxylic acid such as dimethyl terephthalate (about 288 ° C.); ethylene glycol monophenyl ester Teranoacetate (about 231 ° C.) and alkylene glycol monophenyl ether alkanoates such as ethylene glycol monophenyl ether propionate (about 262 ° C.).
The numerical value in parentheses immediately after the name of each solvent is the boiling point under atmospheric pressure.
These (H) high boiling point solvents may be used in combination of two or more.

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

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

  (H) Content of the compound which has an aromatic-hydrocarbon ring and an ester bond in a high boiling point solvent is not specifically limited in the range which does not inhibit the objective of this invention. Typically, the content of the compound having an aromatic hydrocarbon ring and an ester bond is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass with respect to the mass of the (H) high-boiling solvent. % Or more is particularly preferable, and 100% by mass is most preferable.

  (S) Content of the (H) high boiling point solvent in a solvent is 1 to 30 mass%, and preferably 5 to 15 mass%. By using a high-boiling solvent in an amount within this range, (H) the high-boiling solvent hardly remains in the coating film or the cured film while obtaining the desired effect by using the (H) high-boiling solvent, and the machine It is easy to form a cured film having excellent physical properties.

  As long as the object of the present invention is not impaired, the (S) solvent may contain a solvent having a boiling point of more than 300 ° C. under atmospheric pressure, but the (S) solvent is (L) a low boiling point solvent and (H) Preferably it consists only of excitement store solvent.

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

<Other ingredients>
The photosensitive resin composition may contain various additives as needed. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, and a surfactant.

≪Method of forming cured film≫
The cured film is formed by coating the above-mentioned photosensitive resin composition on a substrate to form a coating film,
Exposing the coating film.

First, contact transfer type coating devices such as roll coaters, reverse coaters and bar coaters, spinners (rotary coating devices), non-spin type (non-rotating) coating devices, slit coaters, curtain flow coaters, etc. The photosensitive resin composition is applied using a mold coating device, and the solvent is removed by heat drying or vacuum / vacuum drying as necessary to form a coating film. The material of the substrate is not particularly limited.
When performing high-speed coating, it is preferable to use a non-contact type coating apparatus. For example, even if the Gantry Speed (GSP) of the non-contact type non-spinning type coating apparatus is set in the range of 350 mm / s to 400 mm / s, for example, a good coating film is formed by the photosensitive resin composition according to the present invention. Is done.

Next, the coating film is cured by irradiating the coating film with active energy rays such as ultraviolet rays and excimer laser light. In the case of a cured film to be formed, or a patterned product such as a black column spacer or a black matrix, exposure of the coating film is selectively performed only in a place where it is desired to be cured.
Such position-selective exposure is usually performed using a negative mask.
For the exposure, a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. The amount of exposure varies depending on the composition of the photosensitive resin composition, but is preferably about 10 to 600 mJ / cm ² , for example.

  When the substrate is a TFT substrate or the like on which an element is formed, a black column spacer or the like is formed on the element or at a location facing the element on the substrate that is paired with the substrate on which the element is formed. You may need to In such a case, it is necessary to change the height of the black column spacer between the part where the element is formed and the other part in consideration of the height of the element. Therefore, in such a case, it is preferable to perform exposure through a halftone mask.

  According to the method for forming a black column spacer according to the present invention, a photosensitive resin composition is applied on a substrate to form a photosensitive resin layer, and the photosensitive resin layer is formed according to a predetermined black column spacer pattern. An exposure step of exposing, and a development step of developing the exposed photosensitive resin layer to form a pattern of a black column spacer.

First, in the coating process, a contact transfer type coating device such as a roll coater, reverse coater, bar coater, spinner (rotary coating device), non-rotating coating device, slit coater on the substrate on which the black column spacer is to be formed. Then, the photosensitive resin composition according to the present invention is applied using a non-contact type coating apparatus such as a curtain flow coater, and the solvent is removed by heat drying or vacuum / vacuum drying as necessary, and the photosensitive resin layer Form.
When performing high-speed coating, it is preferable to use a non-contact type coating apparatus. For example, even if the Gantry Speed (GSP) of the non-contact type non-spinning type coating apparatus is set in the range of, for example, 350 mm / s to 400 mm / s, a good coating film is formed by the photosensitive resin composition according to the present invention. Is done.

Next, in the exposure process, the photosensitive resin layer is irradiated with active energy rays such as ultraviolet rays and excimer laser light through a negative mask, and the photosensitive resin layer is partially exposed according to the pattern of the black column spacer. To do. For the exposure, a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. The amount of exposure varies depending on the composition of the photosensitive resin composition, but is preferably about 10 to 600 mJ / cm ² , for example.

  When the substrate is an element formed on a substrate such as a TFT substrate, a black column spacer is formed on the element or at a location facing the element on the substrate that is paired with the substrate on which the element is formed. There may be a need. In such a case, it is necessary to change the height of the black column spacer between the part where the element is formed and the other part in consideration of the height of the element. Therefore, in such a case, it is preferable to perform exposure through a halftone mask. By using the photosensitive resin composition according to the present invention, black column spacers having different heights can be easily formed by performing exposure through a halftone mask.

When exposure of a coating film is performed in a position-selective manner, the exposed coating film is usually developed using a developer.
By developing the exposed coating film, a patterned cured film such as a black column spacer or a black matrix is formed.
The development method is not particularly limited, and an immersion method, a spray method, or the like can be used. Specific examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

  Post-baking is performed on the coating film that has been exposed or exposed and developed, and then cured by heating. Post baking is preferably performed at 150 to 250 ° C. for 15 to 60 minutes.

  When the photosensitive resin composition contains pigment particles, it may be difficult to form a smooth cured film due to the influence of pigment particles or aggregates of pigment particles. If a cured film is formed according to the method, a smooth cured film having a surface roughness Ra of 15 nm or less, preferably less than 10 nm, can be formed even if the photosensitive resin composition contains pigment particles.

[Preparation Example 1]
The synthesis method of the cardo resin (A-1) is as follows.
First, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid Was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by the following transparent formula (a-4) colorless and transparent.

Next, after adding 600 g of 3-methoxybutyl acetate to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained and dissolving, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was gradually heated and reacted at 110 to 115 ° C. for 4 hours. After confirming disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain a cardo resin (A-1). The disappearance of the acid anhydride group was confirmed by IR spectrum.
This cardo resin (A-1) corresponds to the resin represented by the above formula (a-1).

[Example 1, Example 2, and Comparative Examples 1-12]
25 parts by mass of the cardo resin (A-1) obtained in Preparation Example 1, 10 parts by mass of dipentaerythritol hexaacrylate, and 3- (2-methylbenzoyl) -6- [1- (acetoxyimino) as a photopolymerizable compound ) Ethyl] -9-ethyl-9H-carbazole 5 parts by mass and a black pigment dispersion (solid content 60 parts by mass) were dissolved in a solvent so that the solid content concentration was 14% by mass. The photosensitive resin composition of the example and the comparative example was obtained.
The composition of the solvent was 45% by mass of 3-methoxybutyl acetate (MA), 45% by mass of propylene glycol monomethyl ether acetate (PGMEA), and 10% by mass of the additive solvent of the type described in Table 1.

In addition, about the addition solvent of the kind of Table 1, resin precipitation evaluation was performed as follows.
2 parts by mass of the cardo resin (A-1) obtained in Preparation Example 1 was dissolved in 100 parts by mass of the solvent (single) shown in Table 1 and allowed to stand for 3 days to confirm the presence or absence of precipitation. The results are also shown in Table 1, with ○ indicating that there was no precipitation and × indicating that there was no precipitation.

  About the obtained photosensitive resin composition, the smoothness of the cured film and the pigment dispersion stability (viscosity change, change in foreign matter increase / decrease) were evaluated according to the following methods. These evaluation results are shown in Table 1.

[Method for evaluating smoothness of cured film]
The obtained photosensitive resin composition was applied onto a 680 mm × 880 mm glass substrate (thickness 0.7 mm) using a non-spin type coating apparatus TR45000 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), and the pressure was reduced from atmospheric pressure to 65 Pa. It dried and formed the coating film with a film thickness of 1.0 micrometer. Subsequently, an ultraviolet irradiation machine (product name: MPA6000, manufactured by Canon Inc.) was used to irradiate the coating film with ultraviolet rays (exposure amount 100 mJ / cm ² ). The coated film after exposure was developed with a 0.04 mass% KOH aqueous solution at room temperature for 60 seconds, and then post-baked at 230 ° C. for 30 minutes to obtain a cured film.
The obtained cured film surface roughness was measured with a stylus type film thickness measuring device (NSPR1300, manufactured by ULVAC). From the measured surface roughness (Ra (nm)), the quality was evaluated according to the following criteria. The results are also shown in Table 1.
(Smoothness evaluation criteria)
◎: Ra is less than 5 nm to less than 10 nm ○: Ra is 10 nm or more and 15 nm or less Δ: Ra is more than 15 nm and 25 nm or less ×: Ra is more than 25 nm

[Evaluation method of pigment dispersion stability (change in viscosity, change in foreign matter)
The obtained photosensitive resin composition was allowed to stand at 25 ° C. for 30 days, and then the change in viscosity and the change in the number of foreign substances were evaluated according to the following criteria. The change in the number of foreign substances was evaluated by using the formed coating film after forming a coating film after drying under reduced pressure in the same manner as the method for evaluating the smoothness of the cured film. The results are also shown in Table 1.
(Viscosity change evaluation criteria)
○: No increase in viscosity before and after standing for photosensitive resin composition ×: Increased viscosity before and after standing for photosensitive resin composition (evaluation criteria for change in number of foreign substances)
○: No increase in foreign matter before and after leaving the coating after drying under reduced pressure ×: Increase in foreign matter before and after leaving the coating after drying under reduced pressure

  From Examples 1 and 2, the photosensitive resin composition containing a resin having a cardo structure has an aromatic hydrocarbon ring and an ester bond as the (S) solvent, and has a boiling point of 180 ° C. under atmospheric pressure. When the above compound is contained, the precipitation of the resin is suppressed, a smooth cured film can be formed, and the dispersibility of the pigment is also good.

  From Comparative Examples 1 to 12, when the additive solvent is not a compound having an aromatic hydrocarbon ring and an ester bond, or the boiling point of the additive solvent under atmospheric pressure is less than 180 ° C., precipitation of a resin having a cardo structure It can be seen that it is not possible to achieve both the suppression of the above and the formation of a smooth cured film.

[Example 3 and Comparative Examples 13 to 16]
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the composition of the solvent was changed as shown in Table 2.

The obtained photosensitive resin composition was applied at high speed onto a 680 mm × 880 mm glass substrate (thickness 0.7 mm) using a non-spin type coating apparatus TR45000 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), and then from atmospheric pressure to 65 Pa. And dried under reduced pressure to obtain a photosensitive resin composition layer. The applicability by high-speed application and the surface state of the obtained photosensitive resin composition layer were evaluated according to the following criteria. These evaluation results are shown in Table 2.
(Application speed evaluation criteria)
◯: The speed at which liquid breakage or liquid return does not occur is GSP 350 mm / s or more. Δ: The speed at which liquid breakage or liquid return does not occur is GSP 340 mm / s or more and less than 350 mm / s. , GSP 330mm / s or less (surface condition evaluation criteria)
◯: Abnormality and foreign matter are not observed due to bumping due to VCD (vacuum drying) ×: Abnormality and foreign matter due to bumping due to VCD (vacuum drying)

Claims (10)

(A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (S) a solvent,
The (A) alkali-soluble resin includes a resin having a cardo structure,
The (S) solvent includes (L) a low-boiling solvent having a boiling point of less than 180 ° C under atmospheric pressure, and (H) a high-boiling solvent having a boiling point of from 180 ° C to 300 ° C under atmospheric pressure,
The (H) high boiling point solvent includes a compound having an aromatic hydrocarbon ring and an ester bond,
In the (S) solvent, the content of the (H) high boiling point solvent is 1% by mass or more and 30% by mass or less.
Photosensitive resin composition.   The photosensitive resin composition of Claim 1 whose boiling point in the atmospheric pressure of the said (H) high boiling point solvent is 180 degreeC or more and 220 degrees C or less.   3. The compound according to claim 1, wherein the compound having an aromatic hydrocarbon ring and an ester bond is one or more selected from the group consisting of an aliphatic carboxylic acid benzyl ester and a benzoic acid alkyl ester. Photosensitive resin composition.   The photosensitive resin composition of any one of Claims 1-3 whose content of the said (H) high boiling point solvent in the said (S) solvent is 5 mass% or more and 15 mass% or less.   (D) The photosensitive resin composition of any one of Claims 1-4 containing a pigment.   The cured film which consists of hardened | cured material of the photosensitive resin composition of any one of Claims 1-4.   A cured film comprising a cured product of the photosensitive resin composition according to claim 5.   The cured film of Claim 6 or 7 whose surface roughness Ra is 15 nm or less. Applying the photosensitive resin composition according to any one of claims 1 to 5 on a substrate to form a coating film;
Exposing the coating film, and forming a cured film.   The method for forming a cured film according to claim 9, wherein exposure of the coating film is performed position-selectively, and further, the exposed coating film is developed.