KR101988737B1 - Photosensitive resin composition for black column spacer, black column spacer, display device, and forming method for the black column spacer - Google Patents

Abstract

The present invention relates to a photosensitive resin composition capable of forming a black column spacer having a sufficiently high height in the case of performing exposure through a halftone mask, a black column spacer formed using the composition, a black column spacer And a method of forming a black column spacer using the composition.
Specifically, the present invention provides a photosensitive resin composition for a black column spacer comprising an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a light-shielding agent, wherein the resin having a cardo structure and the acrylic resin / RTI >

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition for a black column spacer, a black column spacer, a display device, and a method of forming a black column spacer.

The present invention relates to a photosensitive resin composition for a black column spacer, a black column spacer formed using the composition, a display device having the black column spacer, and a method of 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 to maintain a constant gap (cell gap) between two substrates.

Conventionally, in order to form a spacer, a method of dispersing bead particles as spacers on the entire surface of a substrate has been adopted. However, in this method, it is difficult to form a spacer having a high positional accuracy. Since the beads adhere to the pixel display portion, the contrast of the image and the display quality deteriorate.

Therefore, in order to solve these problems, various methods for forming spacers by photosensitive resin compositions have been proposed. In this method, a photosensitive resin composition is coated on a substrate, exposed through a predetermined mask and then developed to form a spacer such as a column shape, and a spacer can be formed only at a predetermined portion other than the pixel display portion. In recent years, a so-called black column spacer has been proposed in which spacers are shielded by a light-shielding agent such as carbon black (Patent Document 1, etc.).

[Patent Document 1] JP-A-2011-170075

However, in a display device such as a liquid crystal display device, a substrate such as a TFT substrate on which elements are formed is often used. In the case of using the above substrate, it may be necessary to form a black column spacer on the element formed on the substrate, or on the portion facing the element of the substrate mating 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 at the portion where the element is formed and other portions in consideration of the height of the element.

In this case, since the black column spacer having different heights can be formed at one time by changing the exposure amount depending on the place where the black column spacer is formed, it is preferable to perform the exposure through the halftone mask. However, as a result of a study by the present inventors, it has been found that a photosensitive resin composition containing a resin having a cardo structure, which is used in Patent Document 1 as an alkali-soluble resin, It has been found that it is difficult to form a column spacer.

Accordingly, the present invention provides a photosensitive resin composition capable of forming a black column spacer having a sufficiently high height in the case of performing exposure through a halftone mask, a black column spacer formed using the composition, a black column spacer And a method of forming a black column spacer using the composition.

The inventors of the present invention have studied hard to achieve the above object. As a result, in the photosensitive resin composition for a black column spacer containing an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator and a light-shielding agent, a resin comprising a resin having a cardo structure and an acrylic resin as an alkali- And the present invention has been accomplished based on this finding.

Specifically, the present invention provides the following.

A first aspect of the present invention is a method for producing a black column spacer comprising an alkali soluble resin, a photopolymerizable monomer, a photopolymerization initiator and a light shielding agent, wherein the alkali soluble resin comprises a resin having a cardo structure and an acrylic resin Sensitive resin composition.

A second aspect of the present invention is a black column spacer formed from a photosensitive resin composition for a black column spacer related to the first aspect and a third aspect of the present invention is a black column spacer formed from a black column spacer having a black column spacer Device.

A fourth aspect of the present invention is a method for manufacturing a black column spacer, comprising the steps of: applying a photosensitive resin composition for a black column spacer according to the first aspect onto a substrate to form a photosensitive resin layer; And a developing step of developing the exposed photosensitive resin layer to form a pattern of spacers.

According to the present invention, there is provided a photosensitive resin composition capable of forming a black column spacer having a sufficiently high height in the case of performing exposure through a halftone mask, a black column spacer formed using the composition, And a method of forming a black column spacer using the composition.

«Photosensitive resin composition for black column spacer»

The photosensitive resin composition for a black column spacer according to the present invention (hereinafter simply referred to as "photosensitive resin composition") contains an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator and a light- A resin having a cardo structure and an acrylic resin. Each component contained in the photosensitive resin composition according to the present invention will be described below.

The alkali-soluble resin means a resin film having a thickness of 1 mu m formed on a substrate by a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20 mass% and immersed in a KOH aqueous solution having a concentration of 0.05 mass% for 1 minute , And a film thickness of 0.01 占 퐉 or more.

<(A) Alkali-soluble resin>

The photosensitive resin composition according to the present invention contains (A) a resin having (A1) a cardo structure and (A2) an acrylic resin as an alkali-soluble resin. By containing both a resin having a cardo structure (A1) and an acrylic resin (A2), it is possible to form a black column spacer having a sufficiently different height when exposed through a halftone mask. More specifically, by using the (A) alkali-soluble resin which is related to the above, the thickness H of the black column spacer obtained when the photosensitive resin layer made of the photosensitive resin composition having a thickness of 3 탆 is exposed at an exposure amount of 50 mJ / cm ² _The difference ΔH (= H _FT -H _HT ) between the _{FT and} the film thickness H _HT of the black column spacer obtained when exposed at an exposure of 10 mJ / cm ² is 7000 to 8000 Å.

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

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

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

In the formula (a-1), Y ^a represents a residue other than an acid anhydride group (-CO-O-CO-) from ^a dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-undo-methylene tetrahydrophthalic anhydride, chlorodic anhydride, methyltetrahydrophthalic anhydride, And anhydrous glutaric acid.

In the above formula (a-1), Z ^a represents a residue other than a divalent acid anhydride group from a tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride.

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

The mass average molecular weight of the resin (A1) having a cardo structure is preferably 1000 to 40000, more preferably 2,000 to 30,000. Within the above range, sufficient heat resistance and film strength can be obtained while achieving good developability.

As the acrylic resin (A2), those containing a constituent unit derived from (meth) acrylic acid and / or a constituent unit derived from a (meth) acrylic acid ester are used. (Meth) acrylic acid is acrylic acid or (meth) acrylic acid. (Meth) acrylic acid ester is represented by the following formula (a-4), and is not particularly limited as long as it does not hinder the object of the present invention.

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

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 includes a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, A silyl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxyl group, a carboxylate group, a cyano group, A sulfonyl group, a sulfonyl group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, a hydroxyimino group, an alkyl ether group, an alkylthioether group, an aryl ether group , An aryl thioether group, and an amino group (-NH2, -NHR, -NRR ': R and R' each independently represent a hydrocarbon group). The hydrogen atom contained in the substituent may be substituted by a hydrocarbon group. The hydrocarbon group contained in the substituent may be any of straight chain, branched chain and cyclic.

As R ^a4 , an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group is preferable, and these groups may be substituted with a halogen atom, a hydroxyl group, an alkyl group, or a heterocyclic group. When such a group contains 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 straight chain or branched chain, the number of carbon atoms thereof is preferably from 1 to 20, more preferably from 1 to 15, and particularly preferably from 1 to 10. Preferred examples of the 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- , n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, And practical training.

When the alkyl group is a group containing an alicyclic group or an alicyclic group, preferred alicyclic groups contained in the alkyl group include monocyclic alicyclic groups such as cyclopentyl group and cyclohexyl group, adamantyl group, norbornyl group, isobonyl group, tricyclo A tricyclodecyl group, and a tetracyclododecyl group; and the like.

Preferable examples of the (meth) acrylic acid ester in which the alkyl group is an alicyclic group or an alicyclic group include, for example, compounds represented by the following formulas (a4-1) to (a4-7). Among these, compounds represented by the following formulas (a4-3) to (a4-8) are preferable from the standpoint of obtaining a photosensitive resin composition having excellent developability, and the following formulas (a4-3) and Are more preferable.

In the 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, and R ^a6 represents a hydrogen atom or Represents an alkyl group having 1 to 5 carbon atoms. As R ^a5 , a single bond, a linear or branched alkylene group such as methylene, ethyl, propylene, tetramethylene, ethylethylene, pentamethylene, As R ^a6 , for example, methyl group and ethyl group are preferable.

The aryl group in R ^a4 preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. Specific examples of preferred aryl groups include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl and phenanthryl groups.

The aralkyl group in R ^a4 preferably has 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms. Examples of the aralkyl group include benzyl group,? -Methylbenzyl group,?,? - dimethylbenzyl group, phenylethyl group, phenylethenyl group and the like.

As the heterocyclic group in R ^a4 , there can be mentioned a heterocyclic group having 5 or more members including at least one atom of a nitrogen atom, a sulfur atom and an oxygen atom, preferably a 5- to 7-membered ring. This heterocyclic group may contain a condensed ring. Examples of the heterocyclic group include a pyrrolyl group, a pyridyl group, a pyrimidyl group, a furyl group, and a thienyl group.

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

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

Examples of the unsaturated carboxylic acids include monocarboxylic acids such as crotonic acid and the like; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Anhydrides of these dicarboxylic acids; And the like.

Examples of the aryl halide include aryl esters such as aryl acetate, aryl caproate, aryl caprylate, aryl laurate, aryl palmitate, aryl stearate, aryl benzoate, aryl acetoacetate, and aryl aryl; aryloxyethanol; And the like.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2- But are not limited to, ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydroperfuryl vinyl ether Alkyl vinyl ethers such as methyl vinyl ether; Vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl anthranyl ether; And the like.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutylate, vinyl trimethylacetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl Phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-beta-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthoate.

Examples of the styrenes include styrene; And examples thereof include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, Alkyl styrenes such as acetoxymethyl styrene; Alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; Bromostyrene, 4-trifluoromethylstyrene, 4-trifluoromethylstyrene, 4-trifluoromethylstyrene, 4-chlorostyrene, Halostyrenes such as fluoro-3-trifluoromethylstyrene; And the like.

The amount of the constituent unit derived from (meth) acrylic acid and the amount of the constituent unit derived from the (meth) acrylic acid ester in the (A2) acrylic resin is not particularly limited within the range not hindering the object of the present invention. The amount of the constituent unit derived from (meth) acrylic acid in the (A2) acrylic resin is preferably from 5 to 50 mass%, more preferably from 10 to 30 mass%, based on the mass of the acrylic resin. The amount of the constituent unit derived from the (meth) acrylic acid ester in the (A2) acrylic resin is preferably from 10 to 95% by mass, more preferably from 30 to 90% by mass, based on the mass of the acrylic resin.

The sum of the amount of the constituent unit derived from (meth) acrylic acid and the amount of the constituent unit derived from the (meth) acrylic acid ester in the (A2) acrylic resin is not particularly limited within the range not hindering the object of the present invention, Is preferably 5 to 100 mass%, more preferably 10 to 50 mass%, with respect to the mass of the acrylic resin (A2). When the (A2) acrylic resin contains a constituent unit derived from (meth) acrylic acid and a constituent unit derived from a (meth) acrylic acid ester in an amount within this range, a photosensitive resin composition excellent in halftone characteristics can be easily obtained . When the photosensitive resin composition has excellent halftone characteristics, it is easy to form a black column spacer having a height difference sufficiently according to the light transmittance by exposure through a halftone mask.

As the (A2) acrylic resin, those having an unsaturated bond may be used. The method for producing an acrylic resin having an unsaturated bond is not particularly limited. For example, a method of producing a resin containing a carboxyl group such as a resin containing a constituent unit derived from (meth) acrylic acid and a constituent unit derived from a (meth) And a method of reacting at least part of the carboxyl groups of the acrylic resin with an epoxy group-containing unsaturated compound.

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 an unsaturated compound (a-5) having no alicyclic group or an unsaturated compound containing an alicyclic epoxy group (a-6) .

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) acrylic acid epoxyalkyl esters such as 7-epoxyheptyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α- -? - alkyl acrylate epoxy alkyl esters such as ethyl acrylate 6, 7-epoxy heptyl 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 may be used alone or in combination of two or more.

In the (a-6) unsaturated alicyclic epoxy group-containing 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 isobonyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. These unsaturated compounds containing the (a-6) alicyclic epoxy group may be used singly or in combination of two or more.

Examples of the (a-6) alicyclic epoxy group-containing unsaturated compound specifically include compounds represented by the following formulas (a-6-1) to (a-6-16). Among them, the compounds represented by the following formulas (a-6-1) to (a-6-6) are preferable, and the compounds represented by the following formulas (a-6-1) to a-6-4) is more preferable.

R ^a9 represents a hydrogen atom or a methyl group, and R ^a10 represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms; and 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, A hydrocarbon group, and n represents an integer of 0 to 10. R ^{a8 is preferably a} linear or branched alkylene group such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene or hexamethylene. 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- Phenylene group) is preferable.

(A2) When the acrylic resin has an unsaturated bond, the amount of the structural unit having an unsaturated bond in the acrylic resin is preferably from 1 to 20% by mass, more preferably from 1 to 10% by mass, based on the mass of the acrylic resin (A2) Is more preferable. When an acrylic resin containing a constituent unit having a positive unsaturated bond in this range is used as the acrylic resin (A2), it is easy to obtain a photosensitive resin composition having excellent halftone characteristics.

The mass average molecular weight of the (A2) acrylic resin is preferably from 2,000 to 200,000, more preferably from 5,000 to 30,000. When the amount is in the above-mentioned range, there is a tendency that the film forming ability of the photosensitive resin composition and the balance of developability after exposure tends to be easily obtained.

The alkali-soluble resin (A) may contain other conventionally known alkali-soluble resins in addition to the resin (A1) having a cardo structure and the acrylic resin (A2). However, the total proportion of the resin (A1) having a cardo structure and the acrylic resin (A2) in the alkali-soluble resin (A) is preferably 80% by mass or more, more preferably 90% , And most preferably 100 mass%.

The proportion of the resin (A1) having a cardo structure in the above 100 parts by mass of the alkali-soluble resin (A) is preferably 10 to 90 parts by mass, and more preferably 20 to 70 parts by mass. On the other hand, the proportion of the acrylic resin (A2) in the 100 parts by mass of the alkali-soluble resin (A) is preferably 10 to 90 parts by mass, and more preferably 20 to 70 parts by mass.

The ratio of the resin (A1) having a cardo structure to the acrylic resin (A2) is preferably 99: 1 to 1:99, more preferably 95: 5 to 40:60, More preferably 90:10 to 45:55, particularly preferably 85:15 to 50:50, and most preferably 80:20 to 60:40. Within the above range, it is easy to obtain a photosensitive resin composition having good halftone characteristics.

The content of the alkali-soluble resin (A) in the photosensitive resin composition is preferably 20 to 85% by mass, more preferably 30 to 75% by mass, based on the solid content of the photosensitive resin composition. In the above range, there is a tendency that a balance of developability is easily obtained.

&Lt; (B) Photopolymerizable monomer &gt;

The photopolymerizable monomers include monofunctional monomers and polyfunctional monomers. Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (Meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citracon (meth) acrylamide, N-methylol (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl 2-phenoxy-2-hydroxypropyl &lt; / RTI &gt; (Meth) acrylate, trimethylolpropane (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydroperfuryl (Meth) acrylate of 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, phthalic acid derivative, etc. . These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, butylene glycol di (meth) acrylate, neopentylene glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, (Meth) acryloyloxypropyl (meth) acrylate, ethyleneglycol diglycidylether di (meth) acrylate, diethyleneglycol diglycidylether di (meth) acrylate, phthalic acid diglyme (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene (Meth) acrylamide, (meth) acrylamide methylene ether, a condensation product of a polyhydric alcohol and N-methylol (meth) acrylamide, a reaction product of a diisocyanate and 2-hydroxyethyl , And triacrylate formal, and the like. These multifunctional monomers may be used alone or in combination of two or more.

The content of the (B) photopolymerizable monomer is preferably 1 to 30 mass%, more preferably 5 to 20 mass%, based on the solid content of the photosensitive resin composition. When the concentration is in the above range, a balance of sensitivity, developability and resolution tends to be easily obtained.

&Lt; (C) Photopolymerization initiator &gt;

The photo polymerization initiator is not particularly limited, and conventionally known photo polymerization initiators can be used.

Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- 2-methylpropane-1-one, bis (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl- Dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino- Benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, Oxantone, 2-claw Propyloxyoctone, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthone, 2-methylthioxanthone, There may be mentioned, for example, oxides such as oxalic acid, oxalic acid, oxalic acid, oxalic acid, oxalic acid, oxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2- (O-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- Diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole 2 Benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (i.e., 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- P-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyl acetophenone, p-dimethylaminoacetophenone, , alpha -dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, Methoxy triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis ( (Trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6 (Trichloromethyl) -s-triazine, 2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis 4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) Bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy ) Phenyl-s-triazine, 2,4-bis Bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3- IRGACURE OXE02 &quot;, &quot; IRGACURE OXE01 &quot;, &quot; IRGACURE 369 &quot;, & IRGACURE 651 "," IRGACURE 907 "(trade name, manufactured by BASF), and" NCI-831 "(trade name, manufactured by ADEKA). These photopolymerization initiators may be used alone or in combination of two or more.

Among them, it is particularly preferable to use an oxime-based photopolymerization initiator in view of sensitivity, and it is particularly preferable to use an oxime-based photopolymerization initiator having a carbazole skeleton.

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

In the 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.

As the heterocyclic group in R ^c1 , a heterocyclic group having 5 or more members, preferably a 5-membered or 6-membered ring containing at least one atom of a nitrogen atom, a sulfur atom and an oxygen atom can be mentioned. Examples of the heterocyclic group include a nitrogen-containing five-membered ring group such as a pyrrolyl group, an imidazolyl group, and a pyrazolyl group; A nitrogen-containing 6-membered ring group such as a pyridyl group, a pyrazinyl group, a pyrimidyl group, and a pyridazinyl group; A nitrogen-containing oxygen-containing group such as a thiazolyl group and an isothiazolyl group; A nitrogen-containing oxygen group such as an oxazolyl group and an isoxazolyl group, a sulfur containing group such as a thienyl group, a thiopyranyl group and the like; An impurity group such as a furyl group and a pyranyl group; And the like. Among them, it is preferable to include one nitrogen atom or sulfur atom. The heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group containing a condensed ring include a benzothienyl group and the like.

^Examples of the condensed cyclic aromatic group in R ^c1 include a naphthyl group, an anthryl group, and a phenanthryl group. As the aromatic group in R ^c1 , a phenyl group can be exemplified.

The heterocyclic group, the condensed cyclic aromatic group, or the aromatic group may have a substituent. Particularly, when R ^c1 is an aromatic group, it is preferable to have a substituent. Examples of such substituents include -NO ₂ , -CN, -SO ₂ R ^c5 , -COR ^c5 , -NR ^c6 R ^c7 , -R ^c8 , -OR ^c8 , -O-R ^c9 -O-R ^c10 .

R ^c5 each independently represents an alkyl group, which may be substituted with a halogen atom, or 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 the alkylene moiety of the alkyl group and the alkoxy group may be an ether bond, a thioether bond, As shown in Fig. R ^c6 and R ^c7 may combine to form a ring structure. The alkyl group or alkoxy group in R ^c6 and R ^c7 is preferably a group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, And a width period.

As the ring structure which R ^c6 and R ^c7 can bond to each other, a heterocyclic ring can be exemplified. As the heterocyclic ring, there can be mentioned a heterocyclic ring of at least a 5-membered ring containing at least a nitrogen atom, preferably a 5- to 7-membered ring. The heterocyclic ring may contain a condensed ring. Examples of the heterocycle include a piperidine ring, a morpholine ring, and a thiomorpholine ring. Among them, a morpholine ring is preferable.

R ^c8 represents an alkyl group in which a 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 represent an alkyl group, which may be substituted with a halogen atom, or may be interrupted by an ether bond, a thioether bond or an ester bond. The preferable number of carbon atoms and the specific examples thereof are the same as those of R ^c1 .

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

In the 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 , or -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. Of these, the alkylene moiety 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 combine with each other to form a ring structure together with the nitrogen atom.

The alkyl group for R ^c11 and R ^c12 preferably has 1 to 20 carbon atoms, more preferably 1 to 5 carbon atoms. Examples of the 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- n-hexyl group, n-heptyl group, n-octyl group, isooxyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, , And the like. The alkyl group may have a substituent. Examples of the substituent having a substituent include methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl and methoxypropyl.

The alkenyl group for R ^c11 and R ^c12 preferably has 1 to 20 carbon atoms, more preferably 1 to 5 carbon atoms. Examples of the alkenyl group include a linear or branched group such as a vinyl group, an allyl group, a butenyl group, an ethenyl group, and a propynyl group. The alkenyl group may have a substituent. Examples of the substituent include a 2- (benzoxazol-2-yl) ethenyl group and the like.

The aryl group in ^Rc11 and ^Rc12 preferably has 6 to 20 carbon atoms and more preferably 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

The aralkyl group in ^Rc11 and ^Rc12 preferably has 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms. Examples of the aralkyl group include benzyl group,? -Methylbenzyl group,?,? - dimethylbenzyl group, phenylethyl group, phenylethenyl group and the like.

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

Among these R ^c11 and R ^c12 , the alkylene moiety 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.

As the ring structure that R ^c11 and R ^c12 can bond to form, a heterocyclic ring can be mentioned. As the heterocyclic ring, there can be mentioned a heterocyclic ring of at least a 5-membered ring containing at least a nitrogen atom, preferably a 5- to 7-membered ring. The heterocyclic ring may contain a condensed ring. Examples of the heterocycle include a piperidine ring, a morpholine ring, and a thiomorpholine ring.

Of 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. The organic group is preferably 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 heterocyclic group optionally having a substituent. As the substituent, the same groups as those in the case of R ^c1 can be mentioned. 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 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 alkylene groups include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, sec-butylene, n-pentylene, A straight chain or branched chain group. Among them, R ^c13 is most preferably an isopropylene group.

The formula (c-2) of, R ^c14 represents a monovalent organic group represented by -NR ^c15 R ^c16 (R ^c15 and R ^c16 are each independently a monovalent organic group). Among such organic ^groups , it is ^{preferable that} the structure of R ^c14 is represented by the following formula (c-3) in that the solubility of the photo polymerization 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- , tert-pentyl group, and the like. Of these, R ^c17 and R ^{c18 are} most preferably a methyl group.

As the heterocyclic group in R ^c3 , a heterocyclic group having 5 or more members including at least one atom of a nitrogen atom, a sulfur atom and an oxygen atom, preferably a 5-membered ring or a 6-membered ring, may be mentioned. Examples of the heterocyclic group include a nitrogen-containing five-membered ring group such as a pyrrolyl group, an imidazolyl group, and a pyrazolyl group; A nitrogen-containing nitrogen-containing group such as a nitrogen-containing six-membered ring thiazolyl group such as a pyridyl group, a pyrazinyl group, a pyrimidyl group, and a pyridazinyl group, or an isothiazolyl group; A nitrogen-containing oxygen group such as an oxazolyl group and an isoxazolyl group; A thienyl group, and a thiopyranyl group; An impurity group such as a furyl group and a pyranyl group; And the like. Of these, it is preferable to include one nitrogen atom or sulfur atom. The heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group containing a condensed ring include a benzothienyl group and the like.

The heterocyclic group may have a substituent. As the substituent, the same groups as those in the case of R ^c1 can be mentioned.

In the above formula (c-1), R ^c4 represents a monovalent organic group. Of these, an alkyl group having 1 to 5 carbon atoms is preferable. Examples of such 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- , tert-pentyl group, and the like. Of these, R ^c4 is most preferably a methyl group.

As another preferable example of the oxime-based photopolymerization initiator, there can be mentioned a photopolymerization initiator represented by the following formula (c-4) proposed in JP-A-2010-15025.

In 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 each independently represent 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 a heterocyclic group having 2 to 20 carbon atoms. Hydrogen atoms of the alkyl group, aryl group, arylalkyl group and heterocyclic group ^c41 OR, COR ^{c41, c41} SR, NR ^c42 R ^c43, CONR ^c42 R ^c43, -NR ^{c42 c43} -OR, -OCOR -NCOR ^{c42 c43,} -C ( ^{= N-OR c41) -R c42} , -C (= N-OCOR c41) -R c42, CN, halogen atom, -CR = CR ^{c41 c42} R ^c43, -CO-CR = CR ^{c41 c42} R ^c43, a carboxyl group, Or may be further substituted with an epoxy group. R ^c41 , R ^c42 and R ^c43 each independently represent 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 a heterocyclic group having 2 to 20 carbon atoms.

Wherein R ^c31, R ^c32, R ^c33, Rc ^41, groups a methylene of the alkylene portion of the substituent in R ^c42 and R ^c43, an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or May be interrupted 1 to 5 times by urethane bonding. The alkyl moiety of the substituent may be branched or cyclic, the alkyl terminus of the substituent may be an unsaturated bond, R ^c32 and R ^c33 , and R ^c42 and R ^c43 May be combined with each other to form a ring structure.

The formula (c-4) of, R ^c23 and R ^c24 are each ^{independently, 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 combine with one of the carbon atoms of adjacent benzene rings through -X ^c2 - to form a ring structure, or R ^c23 and R ^c24 may combine to form a ring structure.

In the 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 each independently may form a cyclic structure together with any adjacent benzene ring.

In the formula (c-4), R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^{c42 Examples} of the alkyl group in R ^c43 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- - pentyl group, tert-pentyl group and the like.

In the formula (c-4), ^examples of the aryl group in R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 and R ^c43 include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a chlorophenyl group, Anthryl group, phenanthrenyl group and the like.

Examples of the arylalkyl group in R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 and R ^c43 in the above formula (c-4) include a benzyl group, a chlorobenzyl group, A dimethylbenzyl group, a phenylethyl group, and a phenylethenyl group.

Examples of the heterocyclic group in R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 and R ^c43 in the above formula (c-4) include ^pyridyl , ^pyrimidyl , furyl, thienyl, tetrahydrofuryl, A thiazolyl group, an isoxazolyl group, an isoxazolyl group, an isoxazolyl group, a piperazino group, a benzooxazol-2-yl group, a tetrahydropyranyl group, a pyrrolidyl group, an imidazolididyl group, A 5- to 7-membered ring such as a furanyl group, a furfuryl group, a furfuryl group, a furfuryl group, a furfuryl group,

In the formula (c-4), a ring formed by combining R ^c32 and R ^c33 , a ring formed by bonding R ^c42 and R ^c43 together with R ^c23 and an adjacent benzene ring can be formed Examples of the ring include a 5- to 7-membered ring 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 carbon atoms of adjacent benzene rings to form a 5-membered ring structure together with X ^c2 , the photopolymerization initiator has a carbazole skeleton.

Examples of the halogen atom which may be substituted for R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 and R ^c43 in the formula (c-4) and the halogen atom for R ^c24 and R ^c25 include a fluorine atom, Atoms, and iodine atoms.

The methylene group of the alkylene moiety of the substituent may be interrupted one to five 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 couplers to be interrupted may be one kind or two or more types, and in the case of a group capable of being continuously interrupted, two or more groups may be interrupted continuously. The alkyl moiety of the substituent may be branched or cyclic, and the alkyl terminus of the substituent may be an unsaturated bond.

The content of the photopolymerization initiator (C) is preferably 0.5 to 20 parts by mass based on 100 parts by mass of the solid content of the photosensitive resin composition. When the content is in the above range, sufficient heat resistance and chemical resistance can be obtained, coating film forming ability can be improved, and curing defects can be suppressed.

<(D) Shading agent>

The photosensitive resin composition according to the present invention contains a light-shielding agent. As the light-shielding agent, it is preferable to use a black pigment. Examples of the black pigment used as a light shielding agent include metal oxides such as carbon black, a perylene pigment, a silver tin alloy, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, , Metal sulfates or metal carbonates, organic materials, and inorganic pigments. These black pigments may be used in combination of two or more.

As the light-shielding agent (D), it is preferable to include a perylene pigment in that the adhesion of the black column spacer formed by using the photosensitive resin composition to the substrate can be easily improved. The content of the perylene pigment in the light-shielding agent (D) is preferably 85% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass or more with respect to the total mass of the light-shielding agent (D).

Specific examples of the perylene pigments include perylene pigments represented by the following formula (d-1) and perylene pigments represented by the following formula (d-2). As commercial products, products K0084 and K0086 manufactured by BASF, PIGMENT BLACK 21, 30, 31, 32, 33 and 34 and the like can be preferably used.

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

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

The compound represented by the general formula (d-1) and the compound represented by the general formula (d-2) can be synthesized using the method described in, for example, Japanese Patent Application Laid-Open No. 62-1753 and Japanese Patent Publication No. 63-26784 . Namely, a heating reaction is carried out in water or an organic solvent using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines as raw materials. The obtained preparation is re-precipitated in sulfuric acid or recrystallized in water, an organic solvent or a mixed solvent thereof to obtain the desired product.

In order to disperse the perylene-based pigment well in the photosensitive resin composition, it is preferable that the average particle diameter of the perylene-based pigment is 10 to 1000 nm.

The light shielding agent (D) may be used in combination with a pigment of a color such as red, blue, green, yellow or purple for the purpose of adjusting the color tone. The pigment of a color other than the black pigment can be suitably selected from known pigments and used. The amount of the coloring matter other than the black pigment to be used is preferably 15 mass% or less, more preferably 10 mass% or less, with respect to the total mass of the light-shielding agent (D).

The content of the light-shielding agent (D) in the photosensitive resin composition can be appropriately selected within the range not impairing the object of the present invention, and is typically preferably from 5 to 50 mass% based on the solid content of the photosensitive resin composition. By using the light-shielding agent in such a range, it is possible to suppress the defective exposure and curing defects when the photosensitive resin composition is exposed while making the light-shielding property of the black column spacer obtained using the photosensitive resin composition good.

<(E) Light absorber>

The photosensitive resin composition according to the present invention preferably contains a light absorbent. The light absorbing agent is not particularly limited, and those capable of absorbing exposure light can be used. In particular, it is preferable to absorb light in a wavelength range of 200 to 450 nm. Examples thereof include naphthalene compounds, dinaphthalene compounds, anthracene compounds, phenanthroline compounds, and dyes.

Specific examples include cinnamic acid derivatives such as 2-ethylhexyl cinnamate, 2-ethylhexyl paramethoxy cinnamate, isopropyl methoxy cinnamate, methoxy cinnamic acid and soya wheat; naphthol,? -naphthol methyl ether,? -naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene Naphthalene derivatives such as 2,7-dihydroxynaphthalene; anthracene and derivatives thereof such as anthracene and 9,10-dihydroxy anthracene; Dyes such as azo dyes, benzophenone dyes, amino ketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes and p-aminobenzoic acid dyes; And the like. Of these, cinnamic acid derivatives and naphthalene derivatives are preferably used, and cinnamic acid derivatives are particularly preferred. These light absorbers may be used alone or in combination of two or more.

The content of the (E) light absorber is preferably 0.5 to 20 parts by mass based on 100 parts by mass of the solid content of the photosensitive resin composition. By setting the thickness within the above range, it is possible to increase the ratio of the film thickness change when the exposure amount is changed while keeping the fracture strength after curing well.

<(S) Organic solvents>

 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- propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, (Poly) alcohols such as glycol monomethyl ether, tripropylene glycol monoethyl ether and the like, Glycol monomethyl ether; (Poly) alkylene ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, Methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, 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, ethyl pyruvate, , Other esters such as methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; and amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide.

Of these, alkylene glycol monoalkyl ether acetates, alkylene glycol monoalkyl ether acetates, the above-mentioned other ethers, lactic acid alkyl esters and the above-mentioned other esters are preferable, and alkylene glycol monoalkyl ether acetates, One other ether, and the other esters described above are more preferable. These solvents may be used alone or in combination of two or more.

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

<Other components>

The photosensitive resin composition according to the present invention may contain various additives as required. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor, a thermal polymerization inhibitor, a defoaming agent, and a surfactant.

&Lt; Preparation method of photosensitive resin composition &gt;

The photosensitive resin composition according to the present invention is prepared by mixing each of the above components with a stirrer. Further, it may be filtered using a membrane filter or the like so that the prepared photosensitive resin composition becomes uniform.

<< Spacer, display device, method of forming black column spacer >>

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 is provided with a spacer formed from the photosensitive resin composition according to the present invention. Hereinafter, only the method of forming the black column spacer will be described.

A method of forming a black column spacer according to the present invention is a method of forming a black column spacer by applying a photosensitive resin composition according to the present invention onto a substrate to form a photosensitive resin layer and a step of exposing the photosensitive resin layer to a predetermined black column spacer pattern And a developing step of developing the exposed photosensitive resin layer to form a pattern of black column spacers.

First, in the coating step, a non-contact type coating device such as a roll coater, a reverse coater, a bar coater or the like, a contact transfer type coating device such as a spinner (rotary coating device), or a curtain flow coater is used The photosensitive resin composition according to the present invention is applied and, if necessary, dried to remove the solvent to form a photosensitive resin layer.

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

In the case where the substrate is formed on a substrate such as a TFT substrate, there is a case where it is necessary to form a black column spacer on the element or at a position facing the element of the substrate mated 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 at the portion where the element is formed and at other portions in consideration of the height of the element. 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.

Subsequently, in the development step, the exposed photosensitive resin layer is developed with a developing solution to form a black column spacer. The developing method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developer include aqueous solutions such as organic solvents such as monoethanolamine, diethanolamine and triethanolamine, sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

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

[Example]

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

&Lt; Example 1, Example 2 and Comparative Examples 1 to 3 >

Each component shown in Table 1 below was mixed and dissolved in a solvent such that the solid content was 20 mass%, to prepare a photosensitive resin composition. The solvent was adjusted to be 65% by mass of methoxybutyl acetate, 10% by mass of propylene glycol monomethyl ether acetate (PM), and 25% by mass of cyclohexanone in the whole solvent.

[Table 1]

In Table 1, the respective abbreviations each indicate the following, and the numerical values in parentheses are the number of parts (parts by mass) of the solid content in the photosensitive resin composition.

(Alkali-soluble resin)

A-1: A resin (solid content: 55%, solvent: 3-methoxybutyl acetate)

A-2: Acrylic resin having the following constitutional unit (the number of the lower end of each constitutional unit is the molar ratio of each constitutional unit in the total constitutional unit constituting the acrylic resin). The mass average molecular weight of Resin A-2 is 8,000.

A-3: An acrylic resin having an unsaturated bond having the following constitutional unit (the number of the lower end of each constitutional unit is the molar ratio of each constitutional unit in the total constitutional unit constituting the acrylic resin). The weight average molecular weight of Resin A-3 is 8,000.

(Photopolymerizable monomer)

DPHA: dipentaerythritol hexaacrylate

(Photopolymerization initiator)

OXE02: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-

(Light-shielding agent)

(Solid content: 20 mass%, solvent: 3-methoxybutyl acetate) of the following structure was used.

The synthesis method of the resin (A-1) is as follows.

First, 235 g of bisphenol fluorene 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 And the mixture was heated and dissolved at 90 to 100 DEG C while blowing air at a rate of 25 ml / min. Then, the temperature of the solution was gradually elevated while the solution was cloudy, and the solution was completely dissolved by heating at 120 占 폚. At this time, the solution gradually became clear viscous, but stirring was continued. The acid value was measured, and the heating and stirring were continued until it was less than 1.0 mg KOH / g. The acid value required 12 hours to reach the target value. Then, the mixture was cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate represented by the following formula (a-7) which was colorless transparent and solid.

Then, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene-type epoxy acrylate thus obtained and dissolved. Then, 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide The temperature was gradually raised, and the reaction was carried out at 110 to 115 ° C for 4 hours. After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to obtain a resin (A-1). The disappearance of the acid anhydride group was confirmed by IR spectrum. The resin (A-1) corresponds to the resin represented by the formula (a-1).

[Evaluation of OD value]

The photosensitive resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were coated on a 6-inch glass substrate (Dow Corning Co., 1737 glass), and then dried at 90 DEG C for 60 seconds to form a photosensitive resin layer Respectively. Then, this photosensitive resin layer was irradiated with a ghi ray at an exposure dose of 60 mJ / cm ² . Post-baking was performed on a hot plate at 230 캜 for 20 minutes. The film thickness of the formed light-shielding film was three levels of 0.8 μm, 1.0 μm and 1.2 μm. The OD value at each film thickness was measured for the light-shielding film using D200-II (manufactured by Macbeth), and an OD value near 1 μm was calculated by an approximate curve.

The results are shown in Table 2.

[Evaluation of shape]

The photosensitive resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were coated on a 6-inch glass substrate (Dow Corning Co., 1737 glass) and then dried at 90 占 폚 for 60 seconds to form a film having a thickness of 3.0 占 퐉 Of a photosensitive resin layer. Subsequently, the photosensitive resin layer was selectively irradiated with a ghi ray at an exposure dose of 50 mJ / cm ² through a negative mask with a mask size of 30 탆, and was irradiated with a 0.05 wt% KOH aqueous solution at 23 캜 for 70 seconds, Spray-developed to form a black column spacer. Thereafter, post-baking was performed on a hot plate at 230 占 폚 for 20 minutes.

Then, the diameters B at the lowermost portion of the black column spacer after post-baking and the diameters T at the vicinity of the uppermost portion (95% of the thickness from the lowermost portion) were measured and the T / B ratio was calculated by the following formula. &Quot; &amp; cir &amp; &amp;le; &amp;le; 50 &amp;le; The results are shown in Table 2.

T / B ratio = (T / B) x 100

[Evaluation of relative dielectric constant]

The photosensitive resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were coated on a 6-inch silicon wafer and then dried at 90 DEG C for 60 seconds to form a photosensitive resin layer. Then, this photosensitive resin layer was irradiated with a ghi ray at an exposure dose of 60 mJ / cm ² . Post-baking was performed on a hot plate at 230 캜 for 20 minutes. The film thickness of the formed light-shielding film was 1.0 mu m. The relative dielectric constant (value at 1 kHz) of the light-shielding film with respect to the vacuum in the thickness direction of the light-shielding film was measured using a dielectric constant measuring device SSM495 (manufactured by SSM Japan). The results are shown in Table 2.

[Evaluation of Halftone (HT) Characteristic]

The photosensitive resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were coated on a 6-inch glass substrate (Dow Corning Co., 1737 glass) and then dried at 90 占 폚 for 60 seconds to form a film having a thickness of 3.0 占 퐉 Of a photosensitive resin layer. Then, the photosensitive resin layer was selectively irradiated with a ghi ray through a negative mask having a mask size of 30 mu m. The exposure dose was 5 to 50 mJ / cm ² . Then, a black column spacer was formed by spraying at 0.05% by mass of KOH aqueous solution at 23 캜 for 70 seconds. Thereafter, post-baking was performed on a hot plate at 230 占 폚 for 20 minutes.

Then, the difference in height of the black column spacer after the post-baking in the case of the exposure amount of 5 mJ / cm ^{2 and} the case of the 50 mJ / cm ² was determined, and it was determined as an index of the halftone characteristic H. The results are shown in Table 2.

[Evaluation of adhesion]

The photosensitive resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were coated on a 6-inch glass substrate (Dow Corning, 1737 glass), and then dried at 90 占 폚 for 60 seconds to form a film having a thickness of 3.0 占 퐉 Of a photosensitive resin layer. Then, the photosensitive resin layer was selectively irradiated with a ghi ray at an exposure dose of 50 mJ / cm ² through a negative mask having a mask size of 30 탆, sprayed at 23 캜 for 70 seconds using a 0.05 wt% aqueous KOH solution And developed to form a black column spacer. The development time was about 1.5 times the BP based on the time (BP: break point) until the unexposed portion was completely dissolved. Thereafter, post-baking was performed on a hot plate at 230 占 폚 for 20 minutes.

Then, the minimum mask size at which the black column spacer can be formed at an exposure dose of 50 mJ / cm ² was examined to be an index of adhesion. The results are shown in Table 2.

[Table 2]

As can be seen from Table 2, in the case of using the photosensitive resin compositions of Examples 1 and 2 including a resin having a cardo structure and an acrylic resin, the photosensitive resin layer having a thickness of 3 m made of a photosensitive resin composition was coated at 50 mJ / cm ² (= H _FT- H _HT ) between the film thickness H _FT of the black column spacer obtained when exposed at an exposure amount of 10 mJ / cm ² and the film thickness H _HT of the black column spacer obtained when exposed at an exposure amount of 10 mJ / cm ² is 7000 To 8000 ANGSTROM.

That is, according to Table 2, it can be seen that when using the photosensitive resin compositions of Examples 1 and 2, a black column spacer having a large height difference can be easily formed by exposure through a halftone mask.

On the other hand, in the photosensitive resin composition of Comparative Example 1 containing only water having a cardo structure as an alkali-soluble resin, the? H was less than 7000 占 and the halftone property was lowered.

In addition, according to Comparative Examples 2 and 3, it can be seen that the photosensitive resin composition using only acrylic water as an alkali-soluble resin greatly impaired the adhesion of the formed black column spacer to the substrate. Therefore, in Comparative Examples 2 and 3, since the separation of the black column spacer from the substrate, the halftone characteristics could not be evaluated.

Claims (9)

An alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a light-
Wherein the alkali-soluble resin comprises a resin having a cardo structure and an acrylic resin,
Wherein the light-shielding agent is a photosensitive resin composition for a black column spacer comprising a perylene black pigment,
The photosensitive resin layer of the photosensitive resin composition for a black column spacer having a thickness of 3 탆 was exposed at an exposure of 50 mJ / cm ² and exposed to light with a film thickness H _FT of the black column spacer and an exposure dose of 5 mJ / cm ² (= H _FT- H _HT ) between the obtained black column spacer and the film thickness H _HT of the obtained black column spacer is 7000 to 8000 Å. The method according to claim 1,
Wherein the ratio of the resin having the cardo structure to the acrylic resin is 99: 1 to 1:99 on a mass basis. delete The method according to claim 1 or 2,
A photosensitive resin composition for a black column spacer further containing a light absorbent. delete A black column spacer formed from the photosensitive resin composition for a black column spacer of claim 1 or 2. A display device comprising the black column spacer of claim 6. A coating step of coating the photosensitive resin composition for a black column spacer of claim 1 or 2 on a substrate to form a photosensitive resin layer,
An exposure step of exposing the photosensitive resin layer according to a predetermined spacer pattern,
And developing the exposed photosensitive resin layer to form a pattern of spacers. The method of claim 8,
A method of forming a black column spacer in which exposure is performed via a halftone mask in the exposure step.