JP2017151331A - Photosensitive resin composition for black column spacer, black column spacer, display device, and method for forming black column spacer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for forming black column spacer which can form a black column spacer having a sufficient height difference when exposed to light through a halftone mask and can form a black column spacer excellent in adhesion to a substrate; a black column spacer formed using the composition; a display device having the black column spacer; and a method for forming a black column spacer using the composition.SOLUTION: A predetermined amount of one or more (E) basic polymers selected from the group consisting of a graft polymer contains a nitrogen atom and a block copolymer are blended in a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator and (D) a light-shielding agent.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition for black column spacers, a black column spacer formed using the composition, a display device including the black column spacer, and a method for forming a black column spacer using the composition. .

  In a display device such as a liquid crystal display device or an organic EL display device, a spacer is used in order to keep a distance (cell gap) between two substrates constant.

  Conventionally, in order to form a spacer, a method of dispersing bead particles serving as a spacer over the entire surface of a substrate has been adopted. However, this method has a problem in that it is difficult to form a spacer with high positional accuracy, and beads adhere to the pixel display portion, resulting in a decrease in image contrast and display image quality.

  In order to solve these problems, various methods for forming the spacer with the photosensitive resin composition have been proposed. In this method, a photosensitive resin composition is applied onto a substrate, exposed through a predetermined mask, and then developed to form a column-like spacer. A predetermined portion other than a pixel display portion Only the spacer can be formed. In recent years, a so-called black column spacer in which the spacer is provided with a light shielding property by a light shielding agent such as carbon black has also been proposed (Patent Document 1, etc.).

JP 2011-170075 A

  By the way, in a display device such as a liquid crystal display device, a substrate such as a TFT substrate in which elements are formed on the substrate is often used. In the case of using such a substrate, it may be necessary to form a black column spacer on an element formed on the substrate or at a position facing an element of the substrate that is paired with the substrate on which the element is formed. 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.

  In such a case, since the black column spacers having different heights can be formed at a time by changing the exposure amount in accordance with the location where the black column spacers are formed, it is preferable to perform the exposure through a halftone mask. However, the present inventors have examined that a photosensitive resin composition containing a resin having a cardo structure as used in Patent Document 1 as an alkali-soluble resin can be exposed through a halftone mask. It was found that it was difficult to form black column spacers having different heights.

  Moreover, when forming a black column spacer using the photosensitive resin composition described in patent document 1 etc., the adhesiveness to the board | substrate of the formed black column spacer was not necessarily favorable.

  The present invention has been made in view of the above-described problems, and when performing exposure through a halftone mask, a black column spacer having a sufficient height difference can be formed, and adhesion to a substrate can be improved. Photosensitive resin composition for forming black column spacer, black column spacer formed using the composition, display device including the black column spacer, and black column using the composition, capable of forming an excellent black column spacer It is an object to provide a method for forming a spacer.

The inventors of the present invention have made extensive studies to achieve the above object. As a result, a graft copolymer containing a nitrogen atom in a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a light-shielding agent. The present invention has been completed by finding that the above-mentioned problems can be solved by blending one or more basic polymers (E) selected from the group consisting of block copolymers. The block copolymer consists of a first block having a quaternary ammonium base in the side chain and a second block having no quaternary ammonium base, and the block constitution is a first block-second block, or Second block-first block-second block. Moreover, content of (E) basic polymer is 10 mass% or less with respect to the mass of (D) light-shielding agent.
Specifically, the present invention provides the following.

The first aspect of the present invention contains (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a light-shielding agent, and (E) a basic polymer.
(E) the basic polymer is at least one selected from the group consisting of a graft copolymer containing a nitrogen atom and a block copolymer;
The block copolymer comprises a first block having a quaternary ammonium base in the side chain and a second block having no quaternary ammonium base, and the block configuration is a first block-second block, Or second block-first block-second block,
(E) It is the photosensitive resin composition for black column spacers whose content of a basic polymer is 10 mass% or less with respect to the mass of (D) light-shielding agent.

  2nd aspect of this invention is a black column spacer which consists of hardened | cured material of the photosensitive resin composition for black column spacers which concerns on 1st aspect.

  A third aspect of the present invention is a display device including the black column spacer according to the second aspect.

According to a fourth aspect of the present invention, a photosensitive resin layer is formed by applying the photosensitive resin composition for a black column spacer according to the first aspect on a substrate,
Exposure of the photosensitive resin layer according to a predetermined spacer pattern;
And forming a spacer pattern by developing a photosensitive resin layer after exposure.

  According to the present invention, when performing exposure through a halftone mask, a black column spacer that can form a black column spacer that has a sufficient height difference and that has excellent adhesion to a substrate can be formed. A photosensitive resin composition for formation, a black column spacer formed using the composition, a display device including the black column spacer, and a method for forming a black column spacer using the composition can be provided.

≪Photosensitive resin composition for black column spacer≫
The photosensitive resin composition for black column spacers (hereinafter simply referred to as “photosensitive resin composition”) includes (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D A) a light-shielding agent, and (E) a basic polymer.
And (E) a photopolymerizable monomer is 1 or more types selected from the group which consists of the graft copolymer containing a nitrogen atom, and a block copolymer.
The block copolymer consists of a first block having a quaternary ammonium base in the side chain and a second block having no quaternary ammonium base, and the block constitution is a first block-second block, or Second block-first block-second block.
(E) Content of basic polymer is 10 mass% or less with respect to the mass of (D) light-shielding agent.
When the photosensitive resin composition has the above-described configuration, it is possible to form a black column spacer that has excellent adhesion to the substrate and is difficult to peel from the substrate.

Moreover, when forming a black column spacer using the photosensitive resin composition having the above-described configuration, the photosensitive resin layer made of the photosensitive resin composition is exposed through a halftone mask, thereby increasing the height. It is easy to form different black column spacers.
In this case, the photosensitive resin layer made of the photosensitive resin composition is exposed at a predetermined exposure amount with a ghi line, developed with a 0.05% by weight aqueous KOH solution at 25 ° C. for 70 seconds, and then at 230 ° C. 20 minutes, the film thickness of the film thickness 1.5μm or more black column spacer obtained by performing post-baking, the predetermined exposure amount, and the film thickness _{H FT} when a 50mJ / cm ^2, 4.5mJ / The difference ΔH (= H _FT −H _HT ) with the film thickness H _HT when it is cm ² is preferably 2500 to 6000 mm.

  Hereinafter, essential or optional components contained in the photosensitive resin composition will be described.

<(A) Alkali-soluble resin>
The photosensitive resin composition according to the present invention contains (A) an 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 is not particularly limited as long as it satisfies the above requirements. Preferable examples of the alkali-soluble resin include (A1) a resin having a cardo structure and (A2) an acrylic resin.

  (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 is preferably 1000 to 40000, and more preferably 2000 to 30000. By setting it as the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

  (A2) As acrylic resin, what contains the structural unit derived from (meth) acrylic acid and / or the structural unit derived from (meth) acrylic acid ester is used. (Meth) acrylic acid is acrylic acid or methacrylic acid. The (meth) acrylic acid ester is represented by the following formula (a-4) and is not particularly limited as long as the object of the present invention is not impaired.

In the above formula (a-4), R ^a3 is a hydrogen atom or a methyl group, and R ^a4 is a monovalent organic group that does not contain an ethylenic or acetylenic unsaturated bond. This organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

The substituent other than the hydrocarbon group in the organic group of R ^a4 is not particularly limited as long as the effect of the present invention is not impaired, and is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanate group. , Isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, hydroxyimino group, alkyl ether group, an alkyl thioether group, an aryl ether group, aryl thioether group, an amino group (-NH _2, -NHR, -NRR ': R and R ′ each independently represents a hydrocarbon group). The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

R ^a4 is preferably an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups may be substituted with a halogen atom, a hydroxyl group, an alkyl group, or a heterocyclic group. When these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.

  When the alkyl group is linear or branched, the number of carbon atoms is preferably 1-20, more preferably 1-15, and particularly preferably 1-10. Examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec -Pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, An isodecyl group etc. are mentioned.

  When the alkyl group is an alicyclic group or a group containing an alicyclic group, the preferred alicyclic group contained in the alkyl group includes a monocyclic alicyclic group such as a cyclopentyl group and a cyclohexyl group. And a polycyclic alicyclic group such as an adamantyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, and tetracyclododecyl group.

  As a suitable example of the (meth) acrylic acid ester in which the alkyl group is an alicyclic group or an alicyclic group, compounds represented by the following formulas (a4-1) to (a4-7) are exemplified. Can be mentioned. In these, since it is easy to obtain the photosensitive resin composition excellent in developability, the compound represented by following formula (a4-3)-(a4-8) is preferable, and following formula (a4-3) or The compound represented by (a4-4) is more preferable.

In the above formulas (a4-1) to (a4-8), R ^a3 represents a hydrogen atom or a methyl group, R ^a5 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms. , R ^a6 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ^a5 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 ^a6 , for example, a methyl group and an ethyl group are preferable.

As the aryl group for R ^a4, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable. Specific examples of suitable aryl groups include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, anthryl group, phenanthryl group and the like.

The aralkyl group for R ^a4 is preferably one having 7 to 20 carbon atoms, and more preferably one having 7 to 12 carbon atoms. Examples of the aralkyl group include benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group, phenylethyl group, phenylethenyl group and the like.

^Examples of the heterocyclic group for R ^a4 include 5-membered or more, preferably 5- to 7-membered heterocyclic groups containing at least one of a nitrogen atom, a sulfur atom, and an oxygen atom. This heterocyclic group may contain a condensed ring. Examples of the heterocyclic group include pyrrolyl, pyridyl, pyrimidyl, furyl, and thienyl groups.

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

  (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 unsaturated carboxylic acids include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; and anhydrides of these dicarboxylic acids.

  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.

  As vinyl ethers, 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 Examples include phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

  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 amount of the structural unit derived from (meth) acrylic acid and the amount of the structural unit derived from (meth) acrylic acid ester in the (A2) acrylic resin are not particularly limited as long as the object of the present invention is not impaired. . (A2) The amount of the structural unit derived from (meth) acrylic acid in the acrylic resin is preferably from 5 to 50 mass%, more preferably from 10 to 30 mass%, based on the mass of the acrylic resin. Moreover, 10-95 mass% is preferable with respect to the mass of acrylic resin, and, as for the quantity of the structural unit derived from (meth) acrylic acid ester in (A2) acrylic resin, 30-90 mass% is more preferable. .

  (A2) The total of the amount of the structural unit derived from (meth) acrylic acid and the amount of the structural unit derived from (meth) acrylic acid ester in the acrylic resin is particularly within the range not hindering the object of the present invention. Although not limited, 5-100 mass% is preferable with respect to the mass of (A2) acrylic resin, and 10-50 mass% is more preferable. (A2) Photosensitivity excellent in halftone characteristics when the acrylic resin contains a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid in such an amount. It is easy to obtain a functional resin composition. When the photosensitive resin composition is excellent in halftone characteristics, it is easy to form a black column spacer having a sufficient difference in height depending on the light transmittance by exposing through a halftone mask.

  (A2) As the acrylic resin, one having an unsaturated bond can also be used. The method for preparing the acrylic resin having an unsaturated bond is not particularly limited. For example, a resin containing a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid ester, etc. A method of reacting at least part of the carboxyl group of the acrylic resin containing a carboxyl group with an epoxy group-containing unsaturated compound can be mentioned.

  The epoxy group-containing unsaturated compound is not particularly limited as long as it is a compound containing an unsaturated bond and an epoxy group, but (a-5) an epoxy group-containing unsaturated compound having no alicyclic group, or ( a-6) An alicyclic epoxy group-containing unsaturated compound is preferred.

  Examples of the (a-6) epoxy group-containing unsaturated compound having no alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6, (Meth) acrylic acid epoxy alkyl esters such as 7-epoxyheptyl (meth) acrylate; glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α-ethyl acrylic acid Α-alkyl acrylic acid epoxy alkyl esters such as 6,7-epoxyheptyl; and the like. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate are preferable. These (a-6) epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

  (A-6) In the alicyclic epoxy group-containing unsaturated compound, the alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include 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 (a-6) alicyclic epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

  Specifically, examples of the (a-6) alicyclic epoxy group-containing unsaturated compound include compounds represented by the following formulas (a-6-1) to (a-6-16). Among these, in order to moderate the developability of the photosensitive resin composition, compounds represented by the following formulas (a-6-1) to (a-6-6) are preferable, and the following formula (a The compounds represented by -6-1) to (a-6-4) are more preferable.

In the above formula, R ^a3 represents a hydrogen atom or a methyl group, R ^a8 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^a9 represents a hydrogen atom or a methyl group, and R ^a10 Represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10. R ^a8 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. Examples of R ¹³ include 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.

  When the (A2) acrylic resin has an unsaturated bond, the amount of the structural unit having an unsaturated bond in the acrylic resin is 1 to 20% by mass with respect to the mass of the (A2) acrylic resin. Is preferable, and it is more preferable that it is 1-10 mass%. When an acrylic resin containing a structural unit having an unsaturated bond in such an amount is used as the (A2) acrylic resin, it is easy to obtain a photosensitive resin composition having excellent halftone characteristics.

  (A2) The mass average molecular weight of the acrylic resin is preferably 2000 to 200000, 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 alkali-soluble resin may contain other conventionally known alkali-soluble resins other than (A1) the resin having a cardo structure and (A2) the acrylic resin.
However, the total ratio of the resin having the (A1) cardo structure and the (A2) acrylic resin in the (A) alkali-soluble resin is preferably 80% by mass or more, more preferably 90% by mass or more, and 100 Mass% is most preferred.

  (A) In 100 parts by mass of the alkali-soluble resin, the ratio of the resin having the (A1) cardo structure is preferably 10 to 100 parts by mass, and more preferably 20 to 100 parts by mass.

  (A) It is preferable that content of alkali-soluble resin is 20-85 mass% with respect to solid content of the photosensitive resin composition, and it is more preferable that it is 30-75 mass%. By setting it as the above range, there is a tendency that developability is easily balanced.

<(B) Photopolymerizable monomer>
Photopolymerizable monomers include monofunctional monomers and polyfunctional monomers.
Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 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 Examples include (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers can be used alone or in combination of two or more.

  On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 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 (meta Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi 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 ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (Meth) 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 monomers such as ethers, polyhydric alcohols and N-methylol (meth) acrylamide condensates, and triacryl formal. These polyfunctional monomers can be used alone or in combination of two or more.

  (B) It is preferable that content of a photopolymerizable monomer is 1-30 mass% with respect to solid content of the photosensitive resin composition, and it is more preferable that it is 5-20 mass%. By setting it as the above range, it tends to be easy to balance sensitivity, developability, and resolution.

<(C) Photopolymerization initiator>
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, bis (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4- Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic 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, azobisisobu Tyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- ( o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4 ' -Bisdimethylaminobenzophenone (ie, Michler's ketone) 4,4′-bisdiethylaminobenzophenone (ie, ethyl Michler's ketone), 4,4′-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyl Acetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloro Cetophenone, 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 (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s- Triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) ) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (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 , “IRGACURE OXE02”, “IRGACURE OXE01”, “IRGACURE 369”, “IRGACURE 651”, “IRGACURE 907” (trade name: manufactured by BASF), “NCI-831” (trade name: manufactured by ADEKA), and the like. These photopolymerization initiators can be used alone or in combination of two or more.

  Among these, use of an oxime photopolymerization initiator is particularly preferable in terms of sensitivity, and an oxime photopolymerization initiator having a carbazole skeleton is particularly preferable.

  Preferable examples of the oxime photopolymerization initiator include a photopolymerization initiator represented by the following formula (c-1).

In the above formula (c-1), R ^c1 represents a heterocyclic group, a condensed cyclic aromatic group, or an aromatic group, which may have a substituent. R ^{c2 to} R ^c4 each independently represent a monovalent organic group.

^Examples of the heterocyclic group for R ^c1 include 5-membered or more, preferably 5- or 6-membered heterocyclic groups containing at least one of a nitrogen atom, a sulfur atom, and an oxygen atom. Examples of heterocyclic groups include nitrogen-containing 5-membered ring groups such as pyrrolyl, imidazolyl and pyrazolyl groups; nitrogen-containing 6-membered ring groups such as pyridyl, pyrazinyl, pyrimidyl and pyridazinyl groups; thiazolyl and isothiazolyl groups Nitrogen-containing sulfur groups such as oxazolyl groups and isoxazolyl groups; sulfur-containing groups such as thienyl groups and thiopyranyl groups; oxygen-containing groups such as furyl groups and pyranyl groups; Among these, those containing one nitrogen atom or one sulfur atom are preferable. This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group containing a condensed ring include a benzothienyl group.

^Examples of the condensed cyclic aromatic group for R ^c1 include a naphthyl group, an anthryl group, and a phenanthryl group. Moreover, a phenyl group is mentioned as an aromatic group in ^Rc1 .

The heterocyclic group, the condensed cyclic aromatic group, or the aromatic group may have a substituent. In particular, when R ^c1 is an aromatic group, it preferably has a substituent. Examples of such substituent include —NO ₂ , —CN, —SO ₂ R ^c5 , —COR ^c5 , —NR ^c6 R ^c7 , —R ^c8 , —OR ^c8 , —O—R ^c9 —O—R ^{c10, and the} like. Is mentioned.

R ^c5 independently represents an alkyl group, which may be substituted with a halogen atom, and may be interrupted by an ether bond, a thioether bond, or an ester bond. The alkyl group in R ^c5 preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.

R ^c6 and R ^c7 each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, which may be substituted with a halogen atom, and among these, the alkylene group of the alkyl group and the alkoxy group is an ether bond, It may be interrupted by a thioether bond or an ester bond. R ^c6 and R ^c7 may be bonded to form a ring structure. The alkyl group or alkoxy group in R ^c6 and R ^c7 preferably has 1 to 5 carbon atoms. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, methoxy group, ethoxy group And propoxy groups.

A ring structure that can be formed by combining R ^c6 and R ^c7 includes a heterocyclic ring. Examples of the heterocyclic ring include 5-membered or more, preferably 5 to 7-membered heterocyclic rings containing at least a nitrogen atom. This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic ring include piperidine ring, morpholine ring, thiomorpholine ring and the like. Among these, a morpholine ring is preferable.

R ^c8 represents an alkyl group in which part or all of the hydrogen atoms may be substituted with a halogen atom. The alkyl group for R ^c8 preferably has 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.

R ^c9 and R ^c10 each independently represents an alkyl group, which may be substituted with a halogen atom, and may be interrupted by an ether bond, a thioether bond, or an ester bond. The preferred number of carbon atoms and specific examples thereof are the same as those described above for R ^c1 .

Among these, preferable examples of R ^c1 include a pyrrolyl group, a pyridyl group, a thienyl group, a thiopyralyl group, a benzothienyl group, a naphthyl group, and a phenyl group having a substituent.

In the above formula (c-1), R ^c2 represents a monovalent organic group. The organic group is preferably a group represented by -R ^c11 , -OR ^c11 , -COR ^c11 , -SR ^c11 , -NR ^c11 R ^c12 . R ^c11 and R ^c12 each independently represent an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group, which may be substituted with a halogen atom, an alkyl group, or a heterocyclic group, Among them, the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond. R ^c11 and R ^c12 may be bonded to form a ring structure with the nitrogen atom.

As an alkyl group in R ^c11 and R ^c12 , one having 1 to 20 carbon atoms is preferable, and one having 1 to 5 carbon atoms is more preferable. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl. Group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group And a straight chain or branched chain group such as Moreover, this alkyl group may have a substituent. Examples of those having a substituent include a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

As an alkenyl group in R ^c11 and R ^c12 , one having 1 to 20 carbon atoms is preferable, and one having 1 to 5 carbon atoms is more preferable. Examples of alkenyl groups include linear or branched groups such as vinyl, allyl, butenyl, ethenyl, and propynyl groups. Moreover, this alkenyl group may have a substituent. Examples of those having a substituent include 2- (benzoxazol-2-yl) ethenyl group and the like.

As an aryl group in R ^c11 and R ^c12 , those having 6 to 20 carbon atoms are preferable, and those having 6 to 10 carbon atoms are more preferable. Examples of the aryl group include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, anthryl group, phenanthryl group and the like.

As an aralkyl group in R ^c11 and R ^c12 , those having 7 to 20 carbon atoms are preferable, and those having 7 to 12 carbon atoms are more preferable. Examples of the aralkyl group include benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group, phenylethyl group, phenylethenyl group and the like.

^Examples of the heterocyclic group for R ^c11 and R ^c12 include 5-membered or more, preferably 5- to 7-membered heterocyclic groups containing at least one of a nitrogen atom, a sulfur atom, and an oxygen atom. This heterocyclic group may contain a condensed ring. Examples of the heterocyclic group include pyrrolyl, pyridyl, pyrimidyl, furyl, and thienyl groups.

Among these R ^c11 and R ^c12 , the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond.

A ring structure that can be formed by combining R ^c11 and R ^c12 includes a heterocyclic ring. Examples of the heterocyclic ring include 5-membered or more, preferably 5 to 7-membered heterocyclic rings containing at least a nitrogen atom. This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic ring include piperidine ring, morpholine ring, thiomorpholine ring and the like.

Among these, R ^c2 is most preferably a methyl group, an ethyl group, a propyl group, or a phenyl group.

In the above formula (c-1), R ^c3 represents a monovalent organic group. Examples of the organic group include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, a group represented by the following formula (c-2), or a substituent. The heterocyclic group which may have a group is preferable. Examples of the substituent include the same groups as in R ^c1 above. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

In the above formula (c-2), R ^c13 represents an alkylene group having 1 to 5 carbon atoms which may be interrupted by an oxygen atom. Examples of such an alkylene group include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, n-pentylene group, isopentylene group, sec-pentylene group and the like. A linear or branched group is mentioned. Among these, R ^c13 is most preferably an ^isopropylene group.

In the formula (c-2), R ^c14 represents a monovalent organic group represented by —NR ^c15 R ^c16 (R ^c15 and R ^c16 each independently represents a monovalent organic group). Among such organic groups, if the structure of R ^c14 is represented by the following formula (c-3), it is preferable in that the solubility of the photopolymerization initiator can be improved.

In the formula (c-3), R ^c17 and R ^c18 each independently represent an alkyl group having 1 to 5 carbon atoms. Examples of such an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec- Examples thereof include a pentyl group and a tert-pentyl group. Among these, R ^c17 and R ^c18 are most preferably a methyl group.

^Examples of the heterocyclic group for R ^c3 include 5-membered or more, preferably 5-membered or 6-membered heterocyclic groups containing at least one of a nitrogen atom, a sulfur atom, and an oxygen atom. Examples of heterocyclic groups include nitrogen-containing 5-membered ring groups such as pyrrolyl, imidazolyl and pyrazolyl groups; nitrogen-containing 6-membered ring groups such as pyridyl, pyrazinyl, pyrimidyl and pyridazinyl groups; thiazolyl and isothiazolyl groups Nitrogen-containing sulfur groups such as oxazolyl groups and isoxazolyl groups; sulfur-containing groups such as thienyl groups and thiopyranyl groups; oxygen-containing groups such as furyl groups and pyranyl groups; Among these, those containing one nitrogen atom or one sulfur atom are preferable. This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group containing a condensed ring include a benzothienyl group.

Moreover, the heterocyclic group may have a substituent. Examples of the substituent include the same groups as in R ^c1 above.

In the above formula (c-1), R ^c4 represents a monovalent organic group. Among these, an alkyl group having 1 to 5 carbon atoms is preferable. Examples of such an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec- Examples thereof include a pentyl group and a tert-pentyl group. Among these, R ^c4 is most preferably a methyl group.

  Further, another preferred example of the oxime photopolymerization initiator includes a photopolymerization initiator represented by the following formula (c-4) proposed in JP 2010-15025 A.

In the formula (c-4), R ^c21 and R ^c22 each independently represent R ^c31 , OR ^c31 , COR ^c31 , SR ^c31 , CONR ^c32 R ^c33 , or CN.

R ^c31 , R ^c32 , and R ^c33 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or carbon A heterocyclic group having 2 to 20 atoms is shown. Alkyl group, aryl group, arylalkyl group, and a hydrogen atom of the heterocyclic group, further ^{OR c41, COR c41, SR c41} , NR c42 R c43, CONR c42 R c43, -NR c42 -OR c43, -NCOR c42 - ^{OCOR c43, -C (= N-} OR c41) -R c42, -C (= N-OCOR c41) -R c42, CN, halogen ^{atom, -CR c41 = CR c42 R c43} , -CO-CR c41 = CR ^It may be substituted with ^c42 R ^c43 , a carboxyl group, or an epoxy group. R ^{c41, R c 42,} and ^{R c43} are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or carbon A heterocyclic group having 2 to 20 atoms is shown.

Methylene groups in the alkylene moiety of the substituents on the ^{R c31, R c32, R c33} , R c41, R c42, and ^{R c43} are unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or The substituent may be interrupted 1 to 5 times, the alkyl part of the substituent may be branched or cyclic alkyl, and the alkyl terminal of the substituent is an unsaturated bond. At best, ^{also, R c32} and ^{R c33,} and ^{R c 42} and ^{R c43} may form a ring structure, respectively.

In the above formula (c-4), R ^c23 and R ^c24 each independently represent R ^c31 , OR ^c31 , COR ^c31 , SR ^c31 , CONR ^c32 R ^c33 , NR ^c31 COR ^c32 , OCOR ^c31 , COOR ^c31 , SCOR ^c31 , OCSR ^c31 , COSR ^c31 , CSOR ^c31 , CN, a halogen atom, or a hydroxyl group. a and b each independently represent an integer of 0 to 4.
R ^c23 may be bonded to one of the carbon atoms of the adjacent benzene ring via —X ^c2 — to form a ring structure, and R ^c23 and R ^c24 are bonded to form a ring structure. May be.

In the above formula (c-4), X ^c1 represents a single bond or CO.

In the formula (c-4), X ^c2 represents an oxygen atom, a sulfur atom, a selenium atom, CR ^c51 R ^c52 , CO, NR ^c53 , or PR ^c54 . R ^c51 , R ^c52 , R ^c53 , and R ^c54 each independently represent R ^c31 , OR ^c31 , COR ^c31 , SR ^c31 , CONR ^c32 R ^c33 , or CN. R ^c51 , R ^c53 , and R ^c54 may each independently form a ring structure together with any adjacent benzene ring.

In the formula ^(c-4), as the alkyl group in ^{R c31, R c32, R c33} , R c41, R c42, and ^{R c43,} methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl Group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group and the like.

In the formula ^(c-4), the aryl group in ^{R c31, R c32, R c33} , R c41, R c42, and ^{R c43,} a phenyl group, a tolyl group, xylyl group, ethylphenyl group, a chlorophenyl group, a naphthyl Group, anthryl group, phenanthrenyl group and the like.

In the formula ^(c-4), the aryl group in ^{R c31, R c32, R c33} , R c41, R c42, and ^{R c43,} benzyl group, chlorobenzyl group, alpha-methylbenzyl, alpha, alpha -A dimethylbenzyl group, a phenylethyl group, a phenylethenyl group, etc. are mentioned.

In the formula ^(c-4), as the heterocyclic group in ^{R c31, R c32, R c33} , R c41, R c42, and ^{R c43,} pyridyl group, pyrimidyl group, furyl group, a thienyl group, a tetrahydrofuryl group, Dioxolanyl group, benzoxazol-2-yl group, tetrahydropyranyl group, pyrrolidyl group, imidazolidyl group, pyrazolidyl group, thiazolidyl group, isothiazolidyl group, oxazolidyl group, isoxazolidyl group, piperidyl group, piperazyl group, morpholinyl group, etc. A 5- to 7-membered ring is preferable.

In the formula ^(c-4), the ring and ^{R c32} and ^{R c33} may be ^formed by combining the ring and the ^{R c 42} and ^{R c43} may be formed by bonding, and together with the benzene ring ^{to which R c23} is adjacent Examples of the ring that can be formed include 5- to 7-membered rings such as cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, and lactam ring.
When X ^c2 is NR ^c53 and R ^c23 is bonded to one of the adjacent carbon atoms of the benzene ring to form a 5-membered ring structure together with X ^c2 , the photopolymerization initiator has a carbazole skeleton. Become.

In the formula ^(c-4), as the halogen atom in ^{R c31, R c32, R c33} , R c41, R c42, and ^{R c43} which may be substituted halogen atoms, and ^{R c24, R c25,} fluorine atom , Chlorine atom, bromine atom and iodine atom.

  The methylene group of the alkylene part of the substituent may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or a urethane bond. In this case, the linking group to be interrupted may be one type or two or more groups, and in the case of a group that can be interrupted continuously, two or more groups may be interrupted continuously. In addition, the alkyl part of the substituent may have a branched chain or may be a cyclic alkyl, and the alkyl terminal of the substituent may be an unsaturated bond.

  A compound represented by the following formula (c-5) is also preferable as the (C) photopolymerization initiator.

（Ｒ^１は水素原子、ニトロ基又は１価の有機基であり、Ｒ^２及びＲ^３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^２とＲ^３とは相互に結合して環を形成してもよく、Ｒ^４は１価の有機基であり、Ｒ^５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、ｎは０〜４の整数であり、ｍは０又は１である。）

(R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, and R ² and R ³ are each a chain alkyl group which may have a substituent and a cyclic organic which may have a substituent. R ² and R ³ may be bonded to each other to form a ring, R ⁴ is a monovalent organic group, and R ⁵ 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, n is an integer of 0 to 4, and m is 0 or 1.)

In formula (c-5), R ¹ represents a hydrogen atom, a nitro group, or a monovalent organic group. R ¹ is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by — (CO) _m — on the fluorene ring in the formula (c-5). In formula (c-5), the bonding position of R ^{1 to} the fluorene ring is not particularly limited. When the compound represented by the formula (c-5) has one or more of R ^1, from such that the synthesis of compounds of formula (c-5) is easy, of one or more of R ¹ One is preferably bonded to the 2-position in the fluorene ring. When R ¹ is plural, the plural R ¹ may be the same or different.

When R ¹ is an organic group, R ¹ 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 ¹ 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, a substituted Examples include a heterocyclylcarbonyl group which may have a group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

When R ¹ is an alkyl group, number of carbon atoms in the alkyl group is preferably from 1 to 20, 1 to 6 is more preferable. Further, when R ¹ is an alkyl group, it may be linear or branched. Specific examples in the case where R ¹ 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 ¹ 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.

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

When R ¹ 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 ¹ 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 ¹ 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 ¹ 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 ¹ 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 ¹ 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 ¹ is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, and more preferably 2-7. Specific examples in the case where R ¹ 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, Examples include an isononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

When R ¹ is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 to 20, and more preferably 7 to 10. Moreover, when R < ¹ > is a naphthyl alkyl group, 11-20 are preferable and, as for the carbon atom number of a naphthyl alkyl group, 11-14 are more preferable. Specific examples when R ¹ is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples in the case where R ¹ 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 ¹ is a phenylalkyl group or a naphthylalkyl group, R ¹ may further have a substituent on the phenyl group or naphthyl group.

When R ¹ is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, and O, such monocycles, or such monocycles and benzene rings 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 ¹ is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ¹ is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R ¹ is a heterocyclyl group.

When R ¹ is an amino group substituted with an organic group having 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, 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 A naphthyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group, and the like. . Specific examples of these suitable organic groups are the same as those for R ¹ . 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 ¹ further have a substituent, the substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 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 ¹ 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 contained in R ¹ have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, R ¹ is preferably a nitro group or a group represented by R ⁶ —CO— because the sensitivity tends to be improved. R ⁶ 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 a group suitable as R ⁶ 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. Among these groups, R ⁶ is particularly preferably a 2-methylphenyl group, a thiophen-2-yl group, or an α-naphthyl group.
Moreover, it is preferable that R ¹ is a hydrogen atom because transparency tends to be good. When R ¹ is a hydrogen atom and R ⁴ is a group represented by the following formula (R4-2), the transparency tends to be better.

In formula (c-5), R ² and R ³ 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 ² and R ³ may be bonded to each other to form a ring. Among these groups, R ² and R ³ are preferably chain alkyl groups which may have a substituent. When R ² and R ³ are chain alkyl groups which may have a substituent, the chain alkyl group may be a linear alkyl group or a branched alkyl group.

When R ² and R ³ 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 in the case where R ² and R ³ 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 ² and R ³ 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 ² and R ³ are a chain alkyl group 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 ¹ 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 ¹ is a heterocyclyl group. When R ¹ 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 ² and R ³ 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 ² and R ³ are cyclic organic groups, the substituents that the cyclic organic group may have are the same as when R ² and R ³ are chain alkyl groups.

When R ² and R ³ 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 ² and R ³ 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 ² and R ³ 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 benzene rings. 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 ² and R ³ may be bonded to each other to form a ring. The group consisting of the ring formed by R ² and R ³ is preferably a cycloalkylidene group. When R ² and R ³ are bonded to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring.

When the group formed by combining R ² and R ³ 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 ² and R ³ 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 ² and R ³ 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 ² and R ³ have as a substituent.

Preferable specific examples of R ² and R ³ include an alkyl group such as an 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 -Pen Group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group; 2-phenylethyl group, 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 group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl- cycloalkylalkyl groups such as an n-butyl group, a 5-cyclopentyl-n-pentyl group, a 6-cyclopentyl-n-hexyl group, a 7-cyclopentyl-n-heptyl group, and an 8-cyclopentyl-n-octyl group; Methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxycarbonyl- n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl Group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycal Alkoxycarbonylalkyl groups such as nyl-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 ² and R ³ , 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 ⁴ include, similarly to R ¹ , 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. 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, An optionally substituted naphthoxycarbonyl group, an optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group, and an optionally substituted heterocyclyl 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 ¹ . R ⁴ is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, or a phenylthioalkyl group optionally having 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 ¹ may have.

Among organic groups, as R ⁴ , an alkyl group, a cycloalkyl group, an optionally substituted phenyl group, or a cycloalkylalkyl group, 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 ⁴ , 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（Ｒ４−１）及び（Ｒ４−２）中、Ｒ^７及びＲ^８はそれぞれ有機基であり、ｐは０〜４の整数であり、Ｒ^７及びＲ^８がベンゼン環上の隣接する位置に存在する場合、Ｒ^７とＲ^８とが互いに結合して環を形成してもよく、ｑは１〜８の整数であり、ｒは１〜５の整数であり、ｓは０〜（ｒ＋３）の整数であり、Ｒ^９は有機基である。） Having described ^{R 4,} as is ^{R 4,} preferably a group represented by the following formula (R4-1) or (R4-2).

(In formulas (R4-1) and (R4-2), R ⁷ and R ⁸ are each an organic group, p is an integer of 0 to 4, and R ⁷ and R ⁸ are adjacent positions on the benzene ring. R ⁷ and R ⁸ may be bonded to each other to form a ring, q is an integer of 1 to 8, r is an integer of 1 to 5, and s is 0 to (r + 3). ) And R ⁹ is an organic group.)

Examples of the organic group for R ⁷ and R ^{8 in} formula (R4-1) are the same as those for R ¹ . R ⁷ is preferably an alkyl group or a phenyl group. When R ⁷ 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 ⁷ is most preferably a methyl group. When R ⁷ and R ⁸ are combined to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferable examples of the group represented by the formula (R4-1) in which R ⁷ and R ⁸ form a ring include a naphthalen-1-yl group, 1, 2, 3, 4-tetrahydronaphthalen-5-yl group etc. are mentioned. In said formula (R4-1), p 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 (R4-2), R ⁹ is an organic group. Examples of the organic group include the same groups as those described for R ¹ . 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. R ⁹ is preferably exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and among these, a methyl group is more preferable.

  In said formula (R4-2), r is an integer of 1-5, the integer of 1-3 is preferable and 1 or 2 is more preferable. In said formula (R4-2), s is 0- (r + 3), the integer of 0-3 is preferable, the integer of 0-2 is more preferable, and 0 is especially preferable. In said formula (R4-2), q 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 (c-5), R ⁵ 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 ⁵ is an alkyl group include a phenyl group and a naphthyl group. In addition, preferred examples of the substituent that R ¹ may have when it is an aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

In formula (c-5), R ⁵ 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 them, a methyl group or a phenyl group is more preferable among these.

The compounds represented by the formula (c-5) may be used alone or in combination of two or more. When two or more are used, the following (i) to (iii) are preferable.
(I) Compound combination of compounds ^{R 1} is a hydrogen atom and ^{R 1} is a compound which is a nitro group (ii) ^{R 4} is formula (R4-1) and ^{R 4} is formula (R4-2) Combination with compound (iii) Compound in which R ⁴ is formula (R4-1) or formula (R4-2) and compound in which R ⁴ is an alkyl group having 1 to 4 carbon atoms Among them, sensitivity and transmission of cured product From the viewpoint of improving characteristics such as the rate, the combination (i) is preferable, and the combination satisfying the above (i) and (ii) or (iii) is more preferable.

  What is necessary is just to adjust suitably the compounding ratio (mass ratio) of each compound by the combination of said (i)-(iii) according to characteristics, such as target sensitivity, For example, 1: 99-99: 1 are preferable, 10 : 90-90: 10 is more preferable, and 30: 70-70; 30 is still more preferable.

（Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、ｍ、及びｎは、式（ｃ−５）と同様である。ｎは０〜４の整数であり、ｍは０又は１である。） The manufacturing method of the compound represented by Formula (c-5) is not particularly limited. The compound represented by the formula (c-5) preferably represents an oxime group (= N—OH) contained in the compound represented by the following formula (c-6) by ═N—O—COR ⁵ . It is manufactured by the method including the process of converting into the oxime ester group. R ⁵ is the same as ^{R 5} in the formula (c-5).

(R ¹ , R ² , R ³ , R ⁴ , m and n are the same as in formula (c-5). N is an integer of 0 to 4, and m is 0 or 1.)

  Therefore, the compound represented by the above formula (c-6) is useful as an intermediate for synthesis of the compound represented by the formula (c-5).

The method for converting the oxime group (= N—OH) into the oxime ester group represented by ═N—O—COR ⁵ is not particularly limited. Typically, a method of reacting the hydroxyl group in the oxime group with an acylating agent that gives an acyl group represented by —COR ⁵ can be mentioned. Examples of the acylating agent include an acid anhydride represented by (R ⁵ CO) ₂ O and an acid halide represented by R ⁵ COHal (Hal is a halogen atom).

When m is 0, the compound represented by the formula (c-5) can be synthesized according to the following scheme 1, for example. In Scheme 1, a fluorene derivative represented by the following formula (1-1) is used as a raw material. When R ¹ is a nitro group or a monovalent organic group, the fluorene derivative represented by the formula (1-1) is converted into a fluorene derivative substituted at the 9-position with R ² and R ³ by a known method, It can be obtained by introducing the substituent R ¹ . The fluorene derivative substituted at the 9-position with R ² and R ³ is, for example, an alkali metal hydroxide as described in JP-A-06-234668 when R ² and R ³ 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 ⁴ is introduced into the fluorene derivative represented by the formula (1-1) by a Friedel-Crafts acylation reaction, and the fluorene derivative represented by the formula (1-3) can get. The acylating agent for introducing an acyl group represented by —CO—R ⁴ may be a halocarbonyl compound or an acid anhydride. As the acylating agent, a halocarbonyl compound represented by the formula (1-2) is preferable. In formula (1-2), 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 ⁴ in the obtained fluorene derivative represented by the formula (1-3) is converted into a group represented by —C (═N—OH) —R ⁴ . An oxime compound represented by the formula (1-4) is obtained. The method for converting the group represented by —CO—R ⁴ into the group represented by —C (═N—OH) —R ⁴ is not particularly limited, but oximation with hydroxylamine is preferred. An oxime compound of the formula (1-4) and an acid anhydride ((R ⁵ CO) ₂ O) represented by the following formula (1-5) or an acid halide represented by the following formula (1-6) ( A compound represented by the following formula (1-7) can be obtained by reacting R ⁵ COHal and Hal are halogen atoms.

In the formulas (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), and (1-7), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are the same as those in formula (c-5).

In scheme 1, R ⁴ contained in each of formula (1-2), formula (1-3), and formula (1-4) may be the same or different. That is, R ⁴ in Formula (1-2), Formula (1-3), and Formula (1-4) may be chemically modified in the synthesis process shown as Scheme 1. 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 ⁴ may undergo is not limited thereto.

<Scheme 1>

When m is 1, the compound represented by the formula (c-5) can be synthesized according to the following scheme 2, for example. In Scheme 2, a fluorene derivative represented by the following formula (2-1) is used as a raw material. The fluorene derivative represented by the formula (2-1) is represented by —CO—CH ₂ —R ⁴ by a Friedel-Crafts reaction to the compound represented by the formula (1-1) by the same method as in Scheme 1. It is obtained by introducing an acyl group. The acylating agent of the formula (1-8): carboxylic acid halide is preferably represented by ^{_{Hal-CO-CH 2 -R 4}} . Subsequently, the methylene group existing between R ⁴ and the carbonyl group in the compound represented by the formula (2-1) is oximed to obtain a ketoxime compound represented by the following formula (2-3). Although the method for oximation of the methylene group is not particularly limited, a nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following formula (2-2) is reacted in the presence of hydrochloric acid. The method of making it preferable is. Next, a ketoxime compound represented by the following formula (2-3) and an acid anhydride ((R ⁵ CO) ₂ O) represented by the following formula (2-4), or the following formula (2-5) A compound represented by the following formula (2-6) can be obtained by reacting with an acid halide (R ⁵ COHal, Hal is a halogen atom). In the following formulas (2-1), (2-3), (2-4), (2-5), and (2-6), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ is the same as formula (c-5).
When m 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 (c-5).

In scheme 2, R ⁴ contained in each of formula (1-8), formula (2-1), and formula (2-3) may be the same or different. That is, R ⁴ in Formula (1-8), Formula (2-1), and Formula (2-3) may undergo chemical modification in the synthesis process shown as Scheme 2. 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 ⁴ may undergo is not limited thereto.

<Scheme 2>

Preferable specific examples of the compound represented by the formula (c-5) include the following compounds 1 to 41.

  (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, sufficient heat resistance and chemical-resistance can be acquired, a coating-film formation ability can be improved, and hardening failure can be suppressed.

<(D) Shading agent>
The photosensitive resin composition according to the present invention contains a light-shielding agent. A black pigment is preferably used as the light-shielding agent. Black pigments used as light-shielding agents include carbon black, perylene pigments, silver-tin alloys, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxidation Various pigments can be mentioned regardless of organic substances and inorganic substances such as organic substances, metal sulfides, metal sulfates or metal carbonates. These black pigments can be used in combination of two or more.

  (D) As the light-shielding agent, a material containing a perylene pigment is preferable because it can easily improve the adhesion of the black column spacer formed using the photosensitive resin composition to the substrate. (D) The content of the perylene pigment in the light-shielding agent is preferably 85% by weight or more, preferably 90% by weight or more, and particularly preferably 100% by weight or more based on the total weight of (D) the light-shielding agent. .

  Specific examples of the perylene pigment include a perylene pigment represented by the following formula (d-1) and a perylene pigment represented by the following formula (d-2). In addition, commercially available products such as product names K0084 and K0086 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, and 34 can be preferably used.

（式（ｄ−１）中、Ｒ^ｄ１、Ｒ^ｄ２は、それぞれ独立して炭素原子数１〜３のアルキレン基を表し、Ｒ^ｄ３、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、Ｒ^ｄ６は、それぞれ独立して炭素原子数１〜７のアルキレン基を表す。）

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

  For the compound represented by the formula (d-1) and the compound represented by the formula (d-2), for example, the methods described in JP-A-62-21753 and JP-B-63-26784 are used. Can be synthesized. 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.

Moreover, in order to disperse | distribute a perylene pigment favorably in the photosensitive resin composition, it is preferable that the average particle diameter of a perylene pigment is 10-1000 nm.
Moreover, in order to disperse | distribute (D) light-shielding agent uniformly, you may use (G) dispersing agent further. As such a dispersant (G), it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. Moreover, you may use separately the below-mentioned (E) basic polymer as a dispersing agent (G). When carbon black or perylene pigment is used as the inorganic pigment, it is preferable to use an acrylic resin dispersant. In addition, the (E) basic polymer in the present invention is (D) separately from the (G) dispersant for dispersing the light-shielding agent (that is, a light-shielding agent dispersion containing the (D) component and the (G) component) Apart from that, it is a component added to the photosensitive resin composition for the black column spacer.

  In addition, (D) the light-shielding agent can be used in combination with a black pigment and a dye having a hue such as red, blue, green, yellow, and purple for the purpose of adjusting the color tone. A dye having a hue other than the black pigment can be appropriately selected from known dyes. The coloring matter other than the black pigment is preferably used in an amount of 15% by weight or less, more preferably 10% by weight or less based on the total weight of the (D) light-shielding agent.

  The content of the (D) light-shielding agent in the photosensitive resin composition can be appropriately selected within the range not impairing the object of the present invention, and typically 5 to 50 mass based on the solid content of the photosensitive resin composition. % Is preferred. By using an amount of the light-shielding agent in such a range, the black column spacer obtained using the photosensitive resin composition has good light-shielding properties, and the exposure failure or the curing failure when exposing the photosensitive resin composition. It is easy to suppress.

<(E) Basic polymer>
The photosensitive resin composition contains (E) a basic polymer (hereinafter, also referred to as “component (E)”).
Said (E) basic polymer is 1 or more types selected from the group which consists of the graft copolymer containing a nitrogen atom, and a block copolymer.
The graft copolymer containing a nitrogen atom and the block copolymer will be described in detail later.

In the basic polymer, the nitrogen atom is contained in the form of an amino group or a quaternary ammonium base.
The amine value of the basic polymer as component (E) is usually 2 mg-KOH / g or more, preferably 3 mg-KOH / g or more, and usually 100 mg-KOH / g or less, preferably 80 mg-KOH / g or less. .
When the amine value is too low, the basicity is insufficient, and it is difficult to obtain the desired effect by using the component (E).
When the amine value is too high, when used in a liquid crystal display device, the voltage holding ratio of the liquid crystal is lowered, and as a result, display failure may occur.

  Hereinafter, the graft copolymer containing a nitrogen atom and a block copolymer are demonstrated about (E) component.

((E1) Graft copolymer containing nitrogen atom)
(E1) As the graft copolymer containing a nitrogen atom, those having a repeating unit containing a nitrogen atom in the main chain are preferred. Especially, it is preferable to have a repeating unit represented by the following formula (Ia) or / and a repeating unit represented by the following formula (ii).

（式（Ｉ−ａ），（ｉｉ）中、Ｒ^４１は、メチレン、エチレン、プロピレン等の直鎖状又は分岐状の炭素原子数１〜５のアルキレン基を表し、好ましくは炭素原子数２〜３のアルキレン基であり、さらに好ましくはエチレン基である。Ａは水素原子又は下記式（ｉｉｉ）〜（ｖ）のいずれかを表すが、好ましくは下記式（ｉｉｉ）である。

（式（ｉｉｉ）中、Ｗ^１は炭素原子数２〜１０の直鎖状又は分岐状のアルキレン基を表し、中でもブチレン、ペンチレン、ヘキシレン等の炭素原子数４〜７のアルキレン基が好ましい。ｐは１〜２０の整数を表し、好ましくは５〜１０の整数である。）

（式（ｉｖ）中、Ｇ^１は２価の連結基を表し、中でもエチレン、プロピレン等の炭素原子数１〜４のアルキレン基とエチレンオキシ、プロピレンオキシ等の炭素原子数１〜４のアルキレンオキシ基が好ましい。Ｗ^２はエチレン、プロピレン、ブチレン等の直鎖状又は分岐状の炭素原子数２〜１０のアルキレン基を表し、中でもエチレン、プロピレン等の炭素原子数２〜３のアルキレン基が好ましい。Ｇ^２は水素原子又は−ＣＯ−Ｒ^４２（Ｒ^４２はエチル、プロピル、ブチル、ペンチル、ヘキシル等の炭素原子数１〜１０のアルキル基を表し、中でもエチル、プロピル、ブチル、ペンチル等の炭素原子数２〜５のアルキル基が好ましい）を表す。ｑは、１〜２０の整数を表し、好ましくは５〜１０の整数である。）

（式（ｖ）中、Ｗ^３は炭素原子数１〜５０のアルキル基又は水酸基を１〜５有する炭素原子数１〜５０のヒドロキシアルキル基を表し、中でもステアリル等の炭素原子数１０〜２０のアルキル基、モノヒドロキシステアリル等の水酸基を１〜２個有する炭素原子数１０〜２０のヒドロキシアルキル基が好ましい。））

(In the formulas (Ia) and (ii), R ⁴¹ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably 2 to 2 carbon atoms. 3 is an alkylene group, more preferably an ethylene group, and A represents a hydrogen atom or any one of the following formulas (iii) to (v), preferably the following formula (iii).

(In Formula (iii), W ¹ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene, and hexylene is preferable. Represents an integer of 1 to 20, preferably an integer of 5 to 10.)

(In formula (iv), G ¹ represents a divalent linking group, and in particular, an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene and an alkyleneoxy having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy. W ² represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene, butylene, etc. Among them, an alkylene group having 2 to 3 carbon atoms such as ethylene and propylene is particularly preferable. G ² represents a hydrogen atom or —CO—R ⁴² (R ⁴² represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, etc., among which carbon such as ethyl, propyl, butyl, pentyl, etc. An alkyl group having 2 to 5 atoms is preferred.) Q represents an integer of 1 to 20, and preferably an integer of 5 to 10.)

(In formula (v), W ³ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 50 carbon atoms having 1 to 5 hydroxyl groups, and among them, stearyl and the like having 10 to 20 carbon atoms. C1-C20 hydroxyalkyl groups having 1-2 hydroxyl groups such as alkyl groups and monohydroxystearyl are preferred.))

The content of the repeating unit represented by the formula (Ia) or (ii) in the graft copolymer is preferably higher, and is generally 50 mol% or more in total, and preferably 70 mol% or more. The repeating unit represented by the formula (Ia) and the repeating unit represented by the formula (ii) may be both present, and the content ratio is not particularly limited, but is preferably the formula (I It is preferable to contain a larger amount of the repeating unit -a). The total number of repeating units represented by the formula (Ia) or (ii) in the graft copolymer is 1 or more, preferably 10 or more, more preferably 20 or more, and usually 100 or less, preferably 70. Hereinafter, it is more preferably 50 or less. The graft copolymer may contain a repeating unit other than those represented by formulas (Ia) and (ii). Examples of other repeating units include an alkylene group and an alkyleneoxy group. Graft copolymer in the present invention, _-NH 2 its ends -NH ₂ and ^-R 41 ^{(R 41} has the formula (I-a), (ii ) definitive when synonymous) preferably from.

  In the case of the graft copolymer as described above, the main chain may be linear or branched.

  The weight average molecular weight of the graft copolymer measured by GPC is preferably 3,000 or more, particularly 5,000 or more, and preferably 100,000 or less, particularly 50,000 or less. If the mass average molecular weight is less than 3,000, the color material cannot be aggregated, and may increase in viscosity or gel. If it exceeds 100,000, the viscosity itself increases. This is not preferable because the solubility in an organic solvent is insufficient.

  As a method for synthesizing the graft copolymer, a known method can be adopted. For example, a method described in JP-B-63-30057 can be used.

((E2) block copolymer)
The block copolymer consists of a first block having a quaternary ammonium base in the side chain and a second block having no quaternary ammonium base, and the block constitution is a first block-second block, or Second block-first block-second block.
The first block constituting the block copolymer is a quaternary ammonium base, preferably —N ⁺ R ^1a R ^2a R ^3a · Y ⁻ (where R ^1a , R ^2a and R ^3a are each independently a hydrogen atom Or an optionally substituted cyclic or chain hydrocarbon group, or two or more of R ^1a , R ^2a and R ^3a may be bonded to each other to form a cyclic structure. Y ^- is, having a quaternary ammonium base represented by represents) a counter anion.. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

In -N ⁺ R ^1a R ^2a R ^3a , as a cyclic structure formed by combining two or more of R ^1a , R ^2a and R ^3a with each other, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or A condensed ring formed by condensing two of these may be mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following.

（式中、ＲはＲ^１ａ〜Ｒ^３ａのうちいずれかの基を表す。）

(In the formula, R represents any one of R ^{1a to} R ^3a .)

  These cyclic structures may further have a substituent.

As ^R 1a ^{to R 3a} in the ^{-N + R 1a R 2a R 3a} , more preferred are also have an alkyl group, or a substituent of the carbon atoms 1-3 may have a substituent Good phenyl group.

  As the A block, those containing a partial structure represented by the following formula (1) are particularly preferable.

（式（１）中、Ｒ^１ａ、Ｒ^２ａ、Ｒ^３ａは各々独立に、水素原子、又は置換されていてもよい環状若しくは鎖状の炭化水素基を表す。あるいは、Ｒ^１ａ、Ｒ^２ａ及びＲ^３ａのうち２つ以上が互いに結合して、環状構造を形成していてもよい。Ｒ^４ａは、水素原子又はメチル基を表す。Ｑは、２価の連結基を表し、Ｙ⁻は、対アニオンを表す。）

(In Formula (1), R ^1a , R ^2a and R ^3a each independently represent a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, R ^1a , R ^2a and R 3 Two or more of ^3a may be bonded to each other to form a cyclic structure, R ^4a represents a hydrogen atom or a methyl group, Q represents a divalent linking group, and Y ⁻ represents a pair Represents an anion.)

In the above formula (1), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ^5a —, —COO—R ^6a — (where R ^5a and R ^6a is a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R ^7a —O—R ^8a —: R ^7a and R ^8a are each independently an alkylene group; ) And the like, and -COO-R ^6a -is preferable.

Examples of Y ⁻ of the counter anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ^{− and the} like.

  Two or more kinds of partial structures containing the specific quaternary ammonium base as described above may be contained in one first block. In that case, two or more quaternary ammonium base-containing partial structures may be contained in the first block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base may be contained in the 1st block, As an example of this partial structure, the below-mentioned partial structure derived from the (meth) acrylic acid ester monomer, etc. Can be mentioned. The content of the partial structure containing no quaternary ammonium base in the first block is preferably 0 to 50% by mass, more preferably 0 to 20% by mass. Most preferably, is not contained in the first block.

  On the other hand, as the second block constituting the block copolymer, for example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Isopropyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, N, N-dimethylaminoethyl (meth) acrylate, etc. (Meth) acrylic acid ester monomer; (meth) acrylic acid salt monomer such as (meth) acrylic acid chloride; (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N, N-dimethylamino Such as ethylacrylamide Meth) acrylamide monomer; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; N- methacryloyl morpholine, polymer structure obtained by copolymerizing comonomers like.

  The second block is preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following formula (2).

（式（２）中、Ｒ^９ａは、水素原子又はメチル基を表す。Ｒ^１０ａは、置換基を有していてもよい環状又は鎖状のアルキル基、置換基を有していてもよいアリル基、又は置換基を有していてもよいアラルキル基を表す。）

(In Formula (2), R ^9a represents a hydrogen atom or a methyl group. R ^10a represents a cyclic or chain alkyl group which may have a substituent, or an allyl which may have a substituent. Represents an aralkyl group which may have a group or a substituent.)

  Two or more types of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one second block. Of course, the second block may further contain a partial structure other than these. When a partial structure derived from two or more kinds of monomers is present in the second block not containing a quaternary ammonium base, each partial structure is contained in the second block in any form of random copolymerization or block copolymerization. May be. When the second block contains a partial structure other than the partial structure derived from the (meth) acrylic acid ester monomer, the content of the partial structure other than the (meth) acrylic acid ester monomer in the second block is However, it is most preferably 0 to 50% by mass, and more preferably 0 to 20% by mass. However, it is most preferable that a partial structure other than the (meth) acrylic acid ester monomer is not included in the second block.

  The block copolymer is a first block-second block or a second block-first block-second block copolymer type polymer compound composed of such a first block and a second block. Such a block copolymer is prepared, for example, by the living polymerization method shown below.

  The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. In the anion living polymerization method, the polymerization active species is an anion, for example, shown in the following scheme.

の場合、

in the case of,

  In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example.

の場合、

in the case of,

の場合、

in the case of,

  In synthesizing such a block copolymer, JP-A-9-62002 and P.I. Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984), B.R. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K .; Ute, et al, Polym. J. et al. 17, 977 (1985), 18, 1037 (1986), Koichi Right-hand, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Thesis, 46, 189 (1989), M.M. Kuroki, T .; Aida, J .; Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.C. Y. Sogoh, W.H. R. The well-known method as described in Hertler et al, Macromolecules, 20, 1473 (1987) etc. can be employ | adopted.

  (E) Whether the basic polymer is a first block-second block copolymer or a second block-first block-second block copolymer, the first polymer constituting the copolymer The one block / second block ratio (mass ratio) is usually in the range of 1/99 or more, particularly 5/95 or more, and usually 80/20 or less, particularly 60/40 or less.

  The amount of the quaternary ammonium base in 1 g of the first block-second block copolymer and the second block-first block-second block copolymer used in the present invention is usually 0.1 to 10 mmol. It is preferable. Such a block copolymer usually contains an amino group produced in the production process, but its amine value is about 1 to 100 mg-KOH / g. The amine value is a value expressed in mg of KOH corresponding to the acid value after neutralization titration of a basic amino group with an acid.

  Moreover, although the acid value of this block copolymer depends on the presence and type of the acid group that is the basis of the acid value, it is generally preferable that the acid value is low, and is usually 10 mg-KOH / g or less, and its molecular weight is The mass average in terms of polystyrene is usually preferably 1000 or more and 100,000 or less. Within the above range, developability and resolution are improved.

  Moreover, when the photosensitive resin composition contains said block copolymer as (E) component, it is preferable that a photosensitive rough-back resin composition contains phosphate ester with a block copolymer. This improves the solubility during development.

  The phosphate ester may be any of primary to tertiary esters, but primary esters are preferred from the viewpoint of developability. As for the structure of the part couple | bonded with phosphoric acid, the structure which has a hydroxyl group at the terminal represented by polyethers, such as polyester, such as polycaprolactone, and polyethylene glycol, for example is mentioned. These may be a copolymer of polyester and polyether. Further, it may have a double bond such as (meth) acrylate at one end of the polyester chain and / or the polyether chain, and may form a copolymer with another radical polymerizable compound.

  Specifically, the phosphate ester preferably has a partial structure represented by the following structural formula (3).

  Such phosphoric acid esters can be produced, for example, by the methods described in JP-B-50-22536 and JP-A-58-128393.

  The mass average molecular weight of the phosphate ester is usually 200 or more, and usually 5000 or less, preferably 1000 or less. Since this phosphate ester is originally added for the purpose of imparting development solubility, it is not preferable to make it high molecular weight.

  In the photosensitive resin composition, (E) the basic polymer is blended in an amount of 10% by mass or less based on the mass of the (D) light-shielding agent. (E) Although the minimum of the compounding quantity of a basic polymer is not specifically limited, 0.1 mass% or more is preferable with respect to the mass of (D) light-shielding agent, 0.5 mass% or more is more preferable, 1.0 mass % Or more is particularly preferable, and 3% by mass or more is most preferable.

<(F) Light absorber>
The photosensitive resin composition preferably contains a light absorber.
The light absorber is not particularly limited, and a light absorber that can absorb exposure light can be used. In particular, a light absorber that absorbs light in a wavelength region of 200 to 450 nm is preferable. Examples thereof include naphthalene compounds, dinaphthalene compounds, anthracene compounds, phenanthroline compounds, and dyes.

  Specifically, cinnamic acid derivatives such as 2-ethylhexyl cinnamate, 2-ethylhexyl paramethoxycinnamate, isopropyl methoxycinnamate, isoamyl methoxycinnamate; α-naphthol, β-naphthol, α-naphthol methyl ether, α -Naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8 -Naphthalene derivatives such as dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene; anthracene such as anthracene and 9,10-dihydroxyanthracene and derivatives thereof; azo series Fee, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenyl cyanoacrylate dyes, triazine dyes, dyes such as p- aminobenzoic acid dyes; and the like. Among these, cinnamic acid derivatives and naphthalene derivatives are preferably used, and cinnamic acid derivatives are particularly preferably used. These light absorbers can be used alone or in combination of two or more.

  (E) It is preferable that content of a light absorber 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, the ratio of the film thickness change when changing an exposure amount can be enlarged, keeping the fracture strength after hardening favorable.

<(S) Organic solvent>
The photosensitive resin composition according to the present invention preferably contains an organic solvent for dilution. Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, 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, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, di Propylene glycol monomethyl ether, zip (Poly) alkylene glycol monoalkyl ethers such as pyrene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene (Poly) alkylene glycol monoalkyl ether acetates such as glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl Other ethers such as ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Lactic acid alkyl esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyacetic acid Ethyl, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-acetate -Propyl, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, pyruvate Other esters such as ethyl, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methyl-2-pyrrolidone, N, N -Dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutyramide, N, N-diethylacetamide, N, N-diethylformamide, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, Pyridine, N, N, N ′, N′-tetramethylurea, etc. Nitrogen-containing polar organic solvent, and the like.

Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers described above, alkyl lactate esters, and other esters described above are preferable, alkylene glycol monoalkyl ether acetates described above. Other ethers and other esters described above are more preferred. Moreover, it is also preferable that the (S) organic solvent contains a nitrogen-containing polar organic solvent in terms of the solubility of each component, (D) the dispersibility of the light-shielding agent, and the like. As the nitrogen-containing polar organic solvent, N, N, N ′, N′-tetramethylurea is preferable.
These solvents can be used alone or in combination of two or more.

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

<Other ingredients>
The photosensitive resin composition according to the present invention may contain various additives as necessary. 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 for producing photosensitive resin composition>
The photosensitive resin composition which concerns on this invention is manufactured by mixing said each component with a stirrer. In addition, you may filter using a membrane filter etc. so that the prepared photosensitive resin composition may become uniform.
When (A) the alkali-soluble resin, (B) the photopolymerizable monomer, (C) the photopolymerization initiator, (D) the light shielding agent, and (E) the basic polymer are mixed, (D) the light shielding agent. However, it is preferable not to mix | blend with the photosensitive resin composition in the state kneaded with (E) basic polymer.
(D) It is considered that (E) the adsorption of the basic polymer to the light-shielding agent can be suppressed, and the segregation effect of the (E) basic polymer in the photosensitive resin composition film can be enhanced.

≪Spacer, display device, black column spacer formation method≫
The black column spacer according to the present invention is the same as the conventional black column spacer except that it is formed from the photosensitive resin composition according to the present invention. The display device according to the present invention is the same as the conventional display device except that the display device includes a spacer formed from the photosensitive resin composition according to the present invention. Hereinafter, only the method for forming the black column spacer will be described.

A preferred method for forming the black column spacer is:
Forming a photosensitive resin layer (application process) by applying the photosensitive resin composition according to the present invention on a substrate;
Exposure of the photosensitive resin layer according to a predetermined spacer pattern (exposure process);
Forming a pattern of a spacer (developing step) by developing the photosensitive resin layer after exposure.

  First, in the coating process, a contact transfer type coating device such as a roll coater, reverse coater or bar coater, a non-contact type such as a spinner (rotary coating device), a curtain flow coater, or the like is formed on a substrate on which a black column spacer is to be formed. The photosensitive resin composition which concerns on this invention is apply | coated using an application | coating apparatus, a solvent is removed by drying as needed, and the photosensitive resin layer is formed.

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.

  Next, in the development step, the black column spacer is formed by developing the exposed photosensitive resin layer with a developer. 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.

  Thereafter, the black column spacer after development is post-baked and cured by heating. Post baking is preferably performed at 150 to 250 ° C. for 15 to 60 minutes.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.

<Examples 1-3, Comparative Example 1, and Comparative Example 2>
The components (parts by mass) shown in the following Table 1 were mixed, and each component was dispersed and dissolved in a solvent so that the solid content was 20% by mass to prepare a photosensitive resin composition. As the light-shielding agent dispersion, a perylene pigment dispersion dispersed with a dispersant was used. Table 1 describes only the solid content (parts by mass) of the perylene pigment, which is a light shielding agent.
The ratio of the basic polymer in Table 1 is the ratio of the mass of the basic polymer to the mass of the light shielding agent.
The composition of the solvent in the photosensitive resin composition is 10% by mass for methoxybutyl acetate, 10% by mass for N, N, N ′, N′-tetramethylurea, and 80% by mass for propylene glycol monomethyl ether acetate. Adjusted as follows.
As each component shown in Table 1, the following were used.

(Alkali-soluble resin)
A-1: Resin obtained by the following production method

(Photopolymerizable monomer)
DPHA: Dipentaerythritol hexaacrylate

(Photopolymerization initiator)
Compound 6: An oxime ester compound having the following structure.

(Basic polymer)
A basic polymer composed of units of the following formula was used.

The synthesis method of the 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-7) 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 Resin (A-1). The disappearance of the acid anhydride group was confirmed by IR spectrum.
In addition, this resin (A-1) is corresponded to resin represented by the said Formula (a-1).

  Using the obtained photosensitive resin composition, halftone characteristics (ΔH) and pattern adhesion were evaluated according to the following methods. These evaluation results are shown in Table 1.

<Halftone characteristics evaluation method>
A photosensitive resin composition was applied on a 10 cm × 10 cm glass substrate and then dried at 100 ° C. for 120 seconds to form a photosensitive resin layer having a thickness of 2.3 μm. Two photosensitive resin layers formed on the glass substrate were prepared in the same manner.
Next, an exposure amount of 50 mJ / cm ^{2 is applied} to one photosensitive layer resin layer using a mirror projection aligner (TME-150 RTO, manufactured by Santopco Co., Ltd.) through a negative mask having a mask size of 30 μm. Then, selective exposure was performed on the other photosensitive resin layer at an exposure amount of 4.5 mJ / cm ² .
The exposed photosensitive resin layer was spray-developed with an aqueous KOH solution having a concentration of 0.04% by mass at 25 ° C. for 70 seconds to obtain a black column spacer.
The obtained black column spacer was post-baked at 230 ° C. for 20 minutes.
The film thickness (height, H _FT ) of the black column spacer formed at an exposure dose of 50 mJ / cm ² and the film thickness (height, H _HT ) of the black column spacer formed at an exposure dose of 4.5 mJ / cm ² And the value of ΔH was determined according to the following formula.
ΔH (Å) = H _FT -H _HT
When the value of ΔH is 2500 mm or more, it is determined that the halftone characteristics are good.

<Pattern adhesion evaluation method>
A photosensitive resin layer having a film thickness of 2.3 μm was formed by the same method as the halftone characteristic evaluation method.
A mirror projection aligner (TME-150 RTO, manufactured by Santopco Co., Ltd.) is used with an exposure gap of 290 μm and an exposure amount of 4.5 mJ / cm ² through a negative mask for forming a dot pattern with a diameter of 15 μm with respect to the photosensitive resin layer. Then, selective exposure was performed.
The exposed photosensitive resin layer was spray-developed with an aqueous KOH solution having a concentration of 0.04% by mass at 25 ° C. for 70 seconds to obtain a black column spacer.
The exposed photosensitive resin layer was spray-developed with an aqueous KOH solution having a concentration of 0.04% by mass at 25 ° C. for 70 seconds to obtain a black column spacer.
The obtained black column spacer was post-baked at 230 ° C. for 20 minutes.
The formed black column spacer was observed with an optical microscope to evaluate adhesion. The case where peeling from the substrate was observed was judged as x, and the case where peeling from the substrate was not observed was judged as ◯.

From the examples in Table 1, it can be seen that when the photosensitive resin composition contains a predetermined amount of a basic polymer, the photosensitive resin composition has both good halftone characteristics and pattern adhesion.
Further, from Comparative Example 1, when the photosensitive resin composition does not contain a basic polymer, the halftone characteristics are not good, and from Comparative Example 2, the content of the basic polymer in the photosensitive resin composition is excessive. When it is, it turns out that pattern adhesiveness is inferior.

Claims (9)

(A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a light-shielding agent, and (E) a basic polymer,
The basic polymer (E) is at least one selected from the group consisting of a graft copolymer containing a nitrogen atom and a block copolymer,
The block copolymer comprises a first block having a quaternary ammonium base in the side chain and a second block having no quaternary ammonium base, and the block configuration is a first block-second block, Or second block-first block-second block,
The photosensitive resin composition for black column spacers, wherein the content of the (E) basic polymer is 10% by mass or less based on the mass of the (D) light-shielding agent.   The photosensitive resin composition for a black column spacer according to claim 1, wherein the (D) light-shielding agent contains a perylene-based black pigment.   Furthermore, (F) The photosensitive resin composition for black column spacers of Claim 1 or 2 containing a light absorber. The photosensitive resin layer made of the photosensitive resin composition for a black column spacer is exposed at a predetermined exposure amount with a ghi line, developed with a 0.05 mass% KOH aqueous solution at 25 ° C. for 70 seconds, and then 230. ℃ for 20 minutes, the black column spacer above thickness 1.5μm obtained by performing post-baking, the predetermined exposure amount, and the film thickness _{H FT} when a 50mJ / cm ^2, 4.5mJ / cm the difference ΔH ₍₌ H FT _{-H HT)} black column spacer photosensitive resin composition according to any one of claims 1 to 3 which is 2500~6000Å the thickness _{H HT} when it is ^2. For a black column spacer, comprising a mixture of (A) alkali-soluble resin, (B) photopolymerizable monomer, (C) photopolymerization initiator, (D) light-shielding agent, and (E) basic polymer A method for producing a photosensitive resin composition, comprising:
The black column according to any one of claims 1 to 4, wherein the (D) light-shielding agent is not blended with the photosensitive resin composition for a black column spacer in a state of being kneaded with the (E) basic polymer. The manufacturing method of the photosensitive resin composition for spacers.   The black column spacer which consists of hardened | cured material of the photosensitive resin composition for black column spacers of any one of Claim 1 to 4.   A display device comprising the black column spacer according to claim 6. Formation of the photosensitive resin layer by apply | coating the photosensitive resin composition for black column spacers of any one of Claim 1 to 4 on a board | substrate,
Exposure of the photosensitive resin layer according to a predetermined spacer pattern;
Forming a pattern of the spacer by developing the photosensitive resin layer after the exposure.   The method for forming a black column spacer according to claim 8, wherein the exposure is exposure through a halftone mask.