KR20150056060A - Photosensitive resin composition for forming black column spacer - Google Patents

Abstract

In the present invention, provided are a photosensitive resin composition for forming black column spacer, which is used for forming black column spacer having low dielectric constant and has good half tone properties, a method for forming black column spacer using the photosensitive resin composition for forming the black column spacer, a black column spacer formed by using the photosensitive resin composition for forming the black column spacer and a display device including the black column spacer. For this, in the present invention, carbon black is treated to introduce acid groups as a light blocking agent and is mixed with a photosensitive resin composition for forming black column spacer including (A) alkali-soluble resin; (B) photopolymerizable monomers; (C) photopolymerization initiators; and (D) a light blocking agent.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition for forming a black column spacer,

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

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 the spacer with high positional accuracy, and since the bead is attached to the pixel display portion, the contrast of the image and the display quality are deteriorated.

In order to solve these problems, various methods have been proposed for forming spacers from a photosensitive resin composition. 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 columnar spacer. Spacers can be formed only on 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.).

Japanese Patent Application Laid-Open No. 2011-170075

However, a black column spacer formed using the photosensitive resin composition disclosed in Patent Document 1 has a problem of high relative dielectric constant. When the relative dielectric constant of the black column spacer is high, display failure of the display device tends to occur.

In addition, a high light shielding property is required for the black column spacer. Taking this point into consideration, it is preferable to increase the content of carbon black in the photosensitive resin composition described in Patent Document 1. However, in this case, the relative dielectric constant of the formed black column spacer becomes remarkably high.

In addition, 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. When such a substrate is used, it may be necessary to form a black column spacer on the element formed on the substrate or on a portion facing the element of the substrate mating with the substrate on which the element is formed. In this case, it is necessary to change the heights of the black column spacers at the portions where the elements are formed and other portions in consideration of the height of the elements.

In this case, since the black column spacer having different heights can be formed at one time by varying the exposure amount depending on the place where the black column spacer is formed, it is preferable to perform exposure through the halftone mask. As described above, the photosensitive resin composition used for forming the black column spacer is required to have good halftone characteristics capable of forming a black column spacer having a sufficiently high height in the case of performing exposure through a halftone mask.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a photosensitive resin composition for forming a black column spacer capable of forming a black column spacer having a low relative dielectric constant and having good halftone characteristics, , A black column spacer formed by using the photosensitive resin composition for forming the black column spacer, and a display device including the black column spacer.

The present inventors have found that (D) a photosensitive resin composition for forming a black column spacer comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) The present inventors have found that the above problems can be solved by blending the carbon black treated with the carbon black that has been treated.

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

The light-shielding agent (D) is a photosensitive resin composition for forming a black column spacer, which contains carbon black to which an acidic group has been introduced.

A second aspect of the present invention is a black column spacer formed from the photosensitive resin composition for forming a black column spacer according to the first aspect.

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

According to a fourth aspect of the present invention,

A coating step of coating the photosensitive resin composition for forming a black column spacer according to the first aspect on a substrate to form a photosensitive resin layer,

An exposure step of exposing the photosensitive resin layer to a predetermined spacer pattern,

And developing the exposed photosensitive resin layer to form a pattern of spacers.

According to the present invention, there is provided a photosensitive resin composition for forming a black column spacer capable of forming a black column spacer having a low relative dielectric constant and having good halftone characteristics, and a black column spacer using the photosensitive resin composition for forming the black column spacer A black column spacer formed using the photosensitive resin composition for forming the black column spacer, and a display device including the black column spacer.

«Photosensitive resin composition for forming black column spacer»

(A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a light-shielding agent. The photosensitive resin composition for forming a black column spacer (hereinafter simply referred to as " photosensitive resin composition & , And the aforementioned light-shielding agent includes carbon black treated with an acidic group. Each component contained in the photosensitive resin composition according to the present invention will be described below.

<(A) Alkali-soluble resin>

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 wt% and immersed in a KOH aqueous solution having a concentration of 0.05 wt% for 1 minute , And a film thickness of 0.01 占 퐉 or more.

The alkali-soluble resin (A) is not particularly limited as long as it is the above-described alkali-soluble resin, and can be appropriately selected from conventionally known resins. Suitable resins as the (A) alkali-soluble resin include (A1) resins having a cardo structure.

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.

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

The formula (a2) of the R ^a1 are each independently a hydrocarbon group, or a halogen atom, a hydrogen atom, the carbon atom to 1~6, R ^a2 are each independently a hydrogen atom or a methyl group, W is ^a single Or a group represented by the following formula (a-3).

In the formula (a-1), Y ^a represents a residue except for the acid anhydride group (-CO-O-CO-) from the dicarboxylic anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-undo-methylene tetrahydrophthalic anhydride, anhydrous chloridic acid, Phthalic acid, and anhydrous glutaric acid.

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

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

The weight average molecular weight (Mw: measured value by gel permeation chromatography (GPC) in styrene conversion, which is the same in this specification) of the resin having (A1) cardo structure is preferably 1000 to 40000, More preferably 30000. Within the above range, sufficient heat resistance and film strength can be obtained while satisfactory developability is obtained.

In addition, (A2) a copolymer obtained by polymerizing (a1) at least an unsaturated carboxylic acid is also preferably used as the alkali-soluble resin (A) because a black column spacer excellent in breaking strength and adhesion to a substrate can be easily obtained.

Examples of the unsaturated carboxylic acid (a1) include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Anhydrides of these dicarboxylic acids; And the like. Of these, (meth) acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, ease of obtaining water, and the like. These (a1) unsaturated carboxylic acids may be used alone or in combination of two or more.

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

Specifically, examples of (a2) unsaturated compounds containing an alicyclic epoxy group include compounds represented by the following formulas (a2-1) to (a2-16). Among these, compounds represented by the following formulas (a2-1) to (a2-6) are preferable, and compounds represented by the following formulas (a2-1) to (a2-4) are more preferable .

Wherein R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a bivalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ¹³ represents a bivalent hydrocarbon group having 1 to 10 carbon atoms, Represents an integer of 0 to 10. R ¹² is preferably a linear or branched alkylene group such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, and hexamethylene. R ¹³ include, for example, methylene group, ethylene group, propylene group, tetramethylene group, ethyl ethylene, pentamethylene group, hexamethylene group, phenylene group, cyclohexylene _{group, -CH 2 - Ph-CH 2} - ( And Ph represents a phenylene group).

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

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

Specifically, examples of (a3) unsaturated alicyclic group-containing compounds include compounds represented by the following formulas (a3-1) to (a3-7). Among them, the compounds represented by the following formulas (a3-3) to (a3-8) are preferable, and the compounds represented by the following formulas (a3-3) and (a3-4) Do.

Wherein R ²¹ represents a hydrogen atom or a methyl group, R ²² represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ²³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, . R ²² is preferably a single bond, a straight chain or branched alkylene group such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene or hexamethylene. As R ²³ , for example, methyl group and ethyl group are preferable.

The copolymer (A2) is preferably a copolymer of the unsaturated carboxylic acid (a1) and the unsaturated compound containing the alicyclic epoxy group (a2) and the unsaturated compound containing the alicyclic group (a3) Containing unsaturated compound may be polymerized.

(a4) Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl (Meth) acrylate; ? -alkylacrylic acid epoxyalkyl esters such as glycidyl? -ethyl acrylate, glycidyl? -n-propyl acrylate, glycidyl? -n-butyl acrylate, and 6,7-epoxyheptyl? -ethylacrylate; And the like. Of these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate are preferable from the viewpoints of copolymerization reactivity, desirable. These (a4) epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.

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

Examples of the (meth) acrylic esters include linear or branched (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate and t- Chain alkyl (meth) acrylates; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono Perfluoro (meth) acrylate; And the like.

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 allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; Allyloxyethanol; And the like.

Examples of 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, tetrahydrofurfuryl 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 -? - phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthoate.

Examples of the styrenes include styrene; Examples of the monomer include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, , And acetoxymethylstyrene; Alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; But are not limited to, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo- Styrene, and 4-fluoro-3-trifluoromethylstyrene; And the like.

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

When the (A2) copolymer contains the structural unit derived from the (a2) alicyclic epoxy group-containing unsaturated compound and the structural unit derived from the (a4) epoxy group-containing unsaturated compound, the content of (a2) The total of the proportion of the constituent unit derived from the alicyclic epoxy group-containing unsaturated compound and the proportion of the constituent unit derived from the (a4) epoxy group-containing unsaturated compound is preferably 71% by weight or more, more preferably 71 to 95% by weight, By weight to 90% by weight. In particular, the proportion of the constituent unit derived from the (a2) alicyclic epoxy group-containing unsaturated compound in the (A2) copolymer is preferably 71% by weight or more, more preferably 71 to 80% by weight. By setting the proportion of the constituent unit derived from the unsaturated compound containing an alicyclic epoxy group (a2) within the above range, the stability with time of the photosensitive resin composition can be further improved.

When the (A2) copolymer contains (a3) the constituent unit derived from the alicyclic group-containing unsaturated compound, the proportion of the constituent unit derived from the (a3) alicyclic group-containing unsaturated compound in the copolymer (A2) Is preferably 30% by weight, more preferably 5 to 20% by weight.

The weight average molecular weight of the (A2) copolymer is preferably from 2,000 to 200,000, more preferably from 3,000 to 30,000. When the amount is in the above range, the film forming ability of the photosensitive resin composition and the balance of developability after exposure tends to be easy to be obtained.

Examples of the alkali-soluble resin (A) include (A3) a copolymer having at least a constituent unit derived from the (a1) unsaturated carboxylic acid and a constituent unit having a polymerizable moiety with a photopolymerizable monomer (B) Or (A4) a structural unit derived from the (a1) unsaturated carboxylic acid, (a2) the alicyclic epoxy group-containing unsaturated compound and / or the (a4) epoxy group-containing unsaturated compound, And a structural unit having a polymerizable moiety with the component (B) is also preferably used. When the alkali-soluble resin (A) includes the (A3) copolymer or the (A4) copolymer, the adhesion of the photosensitive resin composition to the substrate and the destructive strength after curing of the photosensitive resin composition can be increased.

(A3) copolymers and (A4) copolymers are copolymers of (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrene Or the like may be further copolymerized.

The constituent unit having a polymerizable moiety with the photopolymerizable monomer (B) is preferably an ethylenic unsaturated group as the polymerizable moiety (B) with the photopolymerizable monomer. The copolymerization with such a constituent unit can be carried out by copolymerizing at least part of the carboxy group contained in the polymer containing the constituent unit derived from the unsaturated carboxylic acid (a1) with the (A3) copolymer and the unsaturated carboxylic acid group containing the alicyclic epoxy group-containing unsaturated And / or (a4) an epoxy group-containing unsaturated compound. The copolymer (A4) is preferably a copolymer having a constituent unit derived from the unsaturated carboxylic acid (a1) and a copolymer having a constituent unit derived from (a2) an alicyclic epoxy group-containing unsaturated compound and / or (a4) (A1) an unsaturated carboxylic acid with at least a part of the epoxy group in the molecule.

In the copolymer (A3), the proportion of (a1) constituent units derived from an unsaturated carboxylic acid is preferably 1 to 50% by weight, and more preferably 5 to 45% by weight. In the copolymer (A3), the proportion of the constituent unit having a polymerizable moiety to the photopolymerizable monomer (B) is preferably from 1 to 45% by weight, more preferably from 5 to 40% by weight. When the copolymer (A3) contains each constituent unit in such a ratio, it is easy to obtain a photosensitive resin composition capable of forming a black column spacer having excellent adhesion with a substrate.

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

In the copolymer (A4), the proportion of the constituent unit having a polymerizable moiety to the photopolymerizable monomer (B) accounts for preferably from 1 to 45% by weight, more preferably from 5 to 40% by weight. When the copolymer (A4) contains each constituent unit in such a ratio, it is easy to obtain a photosensitive resin composition capable of forming a black column spacer having excellent adhesion with a substrate.

The weight average molecular weight of the (A3) copolymer and the (A4) copolymer is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000. When the amount is in the above range, the film forming ability of the photosensitive resin composition and the balance of developability after exposure tends to be easy to be obtained.

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

&Lt; (B) Photopolymerizable monomer &gt;

(B) 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) acrylamide, butoxymethoxy Acrylates such as methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic anhydride, itaconic acid, (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl acrylate, Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl Acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, (Meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (Meth) acrylate of 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate and phthalic acid derivatives . 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, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, butyleneglycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol (Meth) acrylate, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane, (Meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene di A reaction product of isocyanate and 2-hydroxyethyl (meth) acrylate, a condensate of methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, polyhydric alcohol and N-methylol Monomer And triacryl amide, and the like. These polyfunctional monomers may be used alone or in combination of two or more.

(B) the photopolymerizable monomer is used in an amount of 100 parts by weight based on 100 parts by weight of the total amount of (A) the content of the alkali-soluble resin, (B) the content of the photopolymerizable monomer, and (C) ) The content of the photopolymerizable monomer is preferably 5 to 50 parts by weight, more preferably 6 to 35 parts by weight, in the photosensitive resin composition. By setting the content of the photopolymerizable monomer (B) within this range, it is easy to form a black column spacer having excellent adhesion to a substrate.

From the viewpoint of the adhesion of the formed black column spacer to the substrate, the content of the photopolymerizable monomer (B) is preferably as small as possible. The photosensitive resin composition contains (D) carbon black to which an acidic group is introduced as a light shielding agent. For this reason, the photosensitive resin composition is in a state easily soluble in a slightly alkaline developing solution even after exposure. This tendency becomes more remarkable when the addition amount of the light shielding agent (D) is increased for the purpose of improving the light shielding property and the like. On the other hand, by lowering the content of the photopolymerizable monomer (B) in the photosensitive resin composition, the solubility of the exposed photosensitive resin composition in an alkaline developing solution is lowered without significantly lowering the sensitivity of the photosensitive resin composition.

When the content of the photopolymerizable monomer (B) is to be reduced, (A) a resin having an unsaturated double bond such as (A1) as the alkali-soluble resin, a photopolymerizable monomer (B) such as (A3) , The film hardness can be made good.

<(C) Photopolymerization initiator>

The photopolymerization initiator is not particularly limited and conventionally known photopolymerization initiators can be used.

Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2- hydroxyethoxy) 2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, Dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino- benzyldimethylketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4- , 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, Hexanethene, octanethene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, Benzene anthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2- mercaptobenzooxazole, 2- Sol, a dimer of 2- (o-chlorophenyl) -4,5-diphenylimidazole, a dimer of 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p- methoxyphenyl) Diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (i.e., Helix ketone), 4,4'-bisdiethylaminobenzophenone (i.e., ethyl Michler's ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzo 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-butylacetophenone, p-dimethylaminoacetophenone, p- Butyldichloroacetophenone,?,? -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, (Trichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl- [2- (5-methylfuran-2-yl) (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- [2- (3, 4-dimethoxyphenyl) (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4- 4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- IRGACURE OXE02 &quot;, &quot; IRGACURE OXE01 &quot;, &quot; IRGACURE 369 &quot;, &quot; IRGACURE 651 &quot;, &quot; IRGACURE OXE01 &quot;, &quot; IRGACURE 907 "(product name: BASF agent)," NCI-831 ": and the like (product name: ADEKA claim). 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 terms of sensitivity. The photopolymerization initiator (C) preferably contains a compound represented by the following formula (c-1) among the oxime-based photopolymerization initiators. By including the compound represented by the following formula (c-1) as the photopolymerization initiator (C) in the photosensitive resin composition, the halftone property of the photosensitive resin composition can be particularly improved.

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

In the formula (c-1), when R ^c1 is a monovalent organic group, R ^c1 is not particularly limited within a range that does not impair the object of the present invention, and is appropriately selected from various organic groups. Preferable examples of R ^{c1 in the} case where R ^c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, A naphthoyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoylcarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent , An amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group. When p is an integer of 2 to 4, R ^c1 may be the same or different. The number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent further having a substituent.

When R ^c1 is an alkyl group, the number of carbon atoms is preferably from 1 to 20, more preferably from 1 to 6. When R ^c1 is an alkyl group, it may be linear or branched. Specific examples of the R ^c1 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, iso-octyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n- And an isodecyl group. When R ^c1 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c1 is an alkoxy group, the number of carbon atoms is preferably from 1 to 20, more preferably from 1 to 6. When R ^c1 is an alkoxy group, it may be a straight chain or branched chain. Specific examples of when R ^c1 is an alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec- N-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, isohexyloxy group, isopentyloxy group, sec- tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group and isodecyloxy group. When R ^c1 is an alkoxy group, the alkoxy group may 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 propoxyoxyethoxyethoxy group, and a methoxy Propyloxy group and the like.

When R ^c1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms thereof is preferably from 3 to 10, and more preferably from 3 to 6. Concrete examples of the case where R ^c1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Concrete examples of the case where R ^c1 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group and a cyclooctyloxy group.

When R ^c1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms thereof is preferably from 2 to 20, more preferably from 2 to 7. Specific examples of the case where R ^c1 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanonyl group, a 2,2-dimethylpropanoyl group, Heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, Decanoyl group, n-hexadecanoyl group, and the like. Specific examples of the case where R ^c1 is a saturated aliphatic acyloxy group include an acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, , n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, Tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

When R ^c1 is an alkoxycarbonyl group, the number of carbon atoms is preferably from 2 to 20, more preferably from 2 to 7. Specific examples of when R ^c1 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, An n-pentyloxycarbonyl group, an n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, an n-hexyloxycarbonyl group, N-heptyloxycarbonyl, n-octyloxycarbonyl, iso-octyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, Decyloxycarbonyl group and the like.

When R ^c1 is a phenylalkyl group, the number of carbon atoms thereof is preferably from 7 to 20, and more preferably from 7 to 10. When R ^c1 is a naphthylalkyl group, the number of carbon atoms thereof is preferably from 11 to 20, and more preferably from 11 to 14. Specific examples of the case where R ^c1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group and a 4-phenylbutyl group. Specific examples of when R ^c1 is a naphthylalkyl group include? -Naphthylmethyl,? -Naphthylmethyl, 2- (? -Naphthyl) ethyl and 2- (? - naphthyl) ethyl groups. When R ^c1 is a phenylalkyl group or a naphthylalkyl group, R ^c1 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c1 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing at least one of N, S and O, but is a heterocyclyl group in which these monocyclic rings or benzene rings are condensed with each other. And when the heterocyclyl group is a condensed ring, the number of rings is 3. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, Benzimidazole, benzothiazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, isoindoline, quinazoline, Phthalazine, cinnoline and quinoxaline. When R ^c1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c1 is an amino group substituted with 1 or 2 organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic group having 2 to 20 carbon atoms A phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, A naphthylalkyl group having from 11 to 20 carbon atoms and a heterocyclyl group. Specific examples of these preferred organic ^groups are the same as R ^c1 . Specific examples of the amino group substituted with 1 or 2 organic groups include a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a n-propylamino group, a di-n-propylamino group, an isopropylamino group, n-propylamino group, n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, And the like.

When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c1 have further substituents, substituents include alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, A saturated aliphatic acyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, A dialkylamino group having an alkyl group, 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 ^c1 further have a substituent, the number of the substituent is not limited to the range not hindering the object of the present invention, but is preferably 1 to 4. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c1 have a plurality of substituents, the plurality of substituents may be the same or different.

R ^c1 is chemically stable, has few steric hindrance, is easy to synthesize an oxime ester compound, or has a high solubility in a solvent. From the viewpoints of a nitro group, an alkyl group having 1 to 6 carbon atoms, An alkoxy group having 1 to 6 carbon atoms and a saturated aliphatic acyl group having 2 to 7 carbon atoms, more preferably a nitro group or alkyl having 1 to 6 carbon atoms, and particularly preferably a nitro group or a methyl group.

R ^c1 where the bond to the phenyl group in the case with respect to the phenyl group that is bonded R ^c1, the position of the binding hand (手) with the main skeleton of the phenyl group and the oxime ester compound No. 1 and the second place the position of the methyl group, Fourth or fifth is preferable, and fifth is more preferable. P is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

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

The substituent of the phenyl group or carbazolyl group in R ^c2 is not particularly limited within the scope of not impairing the object of the present invention. Examples of preferable substituents which the phenyl group or the carbazolyl group may have on the carbon atom include an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, a carbon atom number of 3 A saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, A phenoxy group which may have a substituent, a phenylthio which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl which may have a substituent, a benzoyloxy group which may have a substituent, a carbon which may have a substituent A phenylalkyl group having 7 to 20 atoms, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, A naphthoyloxy group which may have a substituent, a naphthylalkyl group of 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, 2, an amino group substituted with an organic group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group and a cyano group.

When R ^c2 is a carbazolyl group, examples of preferable substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated An aliphatic acyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, A naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having a carbon number of 11 to 20 which may have a substituent, A heterocyclyl group which may be substituted, and a heterocyclylcarbonyl group which may have a substituent. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent which the phenyl group or the carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, The naphthylalkyl group which may have a substituent, the heterocyclyl group which may have a substituent, and the amino group substituted by 1 or 2 organic groups are the same as R ^c1 .

Examples of the substituent in the case where the phenyl group, the naphthyl group and the heterocyclyl group included in the substituent group of the phenyl group or the carbazolyl group in the R ^{c2 further} have a substituent include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; A phenyl group; Naphthyl group; Benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group of 1 to 6 carbon atoms; A dialkylamino group having an alkyl group of 1 to 6 carbon atoms; A morpholin-1-yl group; Piperazin-1-yl group; halogen; A nitro group; And cyano group. When the phenyl group, the naphthyl group and the heterocyclyl group contained in the substituent possessed by the phenyl group or the carbazolyl group further have a substituent, the number of the substituent is not limited within the range not hindering the object of the present invention, but is preferably 1 to 4 . When the phenyl group, the naphthyl group and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

R ^c2 is preferably a group represented by the following formula (c-2) or (c-3), more preferably a group represented by the following formula (c-2) from the standpoint of excellent sensitivity of the photosensitive resin composition, a group represented by the formula (c-2) wherein A is S is particularly preferable.

(In the formula (c-2), R ^c4 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group and a cyano group, A is S or O, and r is an integer of 0 to 4 .)

(In the formula (c-3), R ^c5 and R ^c6 each is a monovalent organic group.)

When R ^c4 in the formula (c-2) is an organic group, it can be selected from various organic groups within the range not hindering the object of the present invention. In the formula (c-2), when R ^c4 is an organic group, preferred examples thereof include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; A phenyl group; Naphthyl group; Benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group of 1 to 6 carbon atoms; A dialkylamino group having an alkyl group of 1 to 6 carbon atoms; A morpholin-1-yl group; Piperazin-1-yl group; halogen; A nitro group; And cyano group.

Among R ^c4 , a benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A nitro group is preferable, a benzoyl group; A naphthoyl group; A 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; More preferred is a 4- (phenyl) phenylcarbonyl group.

In the formula (c-2), r is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When r is 1, and R ^c4 is a position at which the bond to the phenyl group R ^c4 is combined preferably in the para position relative to the bonding hands binding to the oxygen atom or a sulfur atom.

R ^c5 in the formula (c-3) can be selected from various organic groups to the extent that the object of the present invention is not impaired. Preferable examples of R ^c5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, , A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, A naphthoyl group, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having a carbon number of 11 to 20 which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent .

R ^c5 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an ethyl group.

R ^c6 in the formula (c-3) is not particularly limited within a range that does not impair the object of the present invention and can be selected from various organic groups. Specific examples of the group represented by R ^c6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclyl group which may have a substituent. As R ^c6 , among these groups, a phenyl group which may have a substituent is more preferable, and a 2-methylphenyl group is particularly preferable.

When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c4 , R ^c5 or R ^c6 further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carbon atom A saturated aliphatic acyl group having a number of 2 to 7, an alkoxycarbonyl group having a carbon number of 2 to 7, a saturated aliphatic acyloxy group having a carbon number of 2 to 7, a monoalkylamino group having an alkyl group having a carbon number of 1 to 6, A dialkylamino group having an alkyl group having a number of 1 to 6, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group and a cyano group. When the phenyl group, the naphthyl group and the heterocyclyl group contained in R ^c4 , R ^c5 or R ^c6 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. desirable. When the phenyl group, the naphthyl group and the heterocyclyl group contained in R ^c4 , R ^c5 or R ^c6 have plural substituents, the plural substituents may be the same or different.

R ^c3 in the formula (c-1) is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have a substituent. When R ^c3 is a phenyl group which may have a substituent, the substituent that the phenyl group may have is the same as R ^c1 described above. When R ^c3 is a phenyl group which may have a substituent, the phenyl group may have two or more substituents. In this case, the substituents of the phenyl group may be the same or different. As R ^c3 , a methyl group or an ethyl group is preferable, and a methyl group is more preferable. When R ^c3 is a methyl group, the photopolymerization initiator made of the compound represented by the formula (c-1) is particularly excellent in sensitivity.

The oxime ester compound represented by formula (c-1) can be synthesized, for example, according to Synthesis Scheme 1 below when q is 0. Specifically, an aromatic compound represented by the following formula (1-1) is acylated by a Friedel-Craft reaction using a halocarbonyl compound represented by the following formula (1-2) to obtain a ketone represented by the following formula (1-3) (1-4) is obtained by oxymethylating the obtained ketone compound (1-3) with hydroxylamine to obtain an oxime compound represented by the following formula (1-4) (R ^c3 CO) ₂ O) represented by the following formula (1-7) or an acid halide (R ^c3 COHal and Hal: halogen) represented by the following formula (1-6) Oxime ester compound can be obtained. Hal in the following formula (1-2) is halogen, and in the following formulas (1-1), (1-2), (1-3), (1-4) , R ^c1 , R ^c2 , R ^c3 And p are the same as in the formula (1).

<Synthetic Plans 1>

The oxime ester compound represented by the formula (c-1) can be synthesized, for example, according to the following synthesis scheme 2 when q is 1. Specifically, a ketone compound represented by the following formula (2-1) is reacted with a nitrite (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following formula (2-2) (2-3) and an acid anhydride ((R ^c3 CO) ₂ O) represented by the following formula (2-4) or a salt of an acid anhydride represented by the following formula An oxime ester compound represented by the following formula (2-6) can be obtained by reacting an acid halide (R ^c3 COHal, Hal: Halogen) represented by the formula (2-5). In the following formulas (2-1), (2-3), (2-4), (2-5) and (2-6), ^Rc1 , ^Rc2 , ^Rc3 And p are the same as in the formula (1).

&Lt; Synthesis Plan 2 &gt;

When the oxime ester compound represented by the formula (c-1) has q of 1, R ^c1 is a methyl group, R ^c1 is bonded to the para position with respect to the methyl group bonded to the benzene ring to which R ^c1 is bonded, For example, the compound represented by the following formula (2-7) may be synthesized by oximation and acylation in the same manner as in Synthesis Plans 1. In the following formula (2-7), R ^c2 is the same as in formula (c-1).

Among the oxime ester compounds represented by the formula (c-1), particularly preferred compounds are the following compounds.

The content of the photopolymerization initiator (C) is preferably 0.5 to 20 parts by weight based on 100 parts by weight of the solid content of the photosensitive resin composition. By setting the ratio within the above range, it is easy to form a black column spacer having excellent heat resistance and chemical resistance, and the coating film forming ability of the photosensitive resin composition can be improved, and curing defects can be suppressed.

<(D) Shading agent>

The photosensitive resin composition according to the present invention includes (D) a light-shielding agent since it is for forming a black column spacer. (D) The light-shielding agent contains carbon black treated with an acidic group. The acid group introduced into the carbon black is a functional group which indicates acidity by definition of Bronsted. Specific examples of the acidic group include a carboxy group, a sulfonic acid group, and a phosphoric acid group. The acid group introduced into the carbon black may form a salt. The cation forming the acidic group and the salt is not particularly limited within the range not hindering the object of the present invention. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions and the like, and alkali metal ions such as sodium ion, potassium ion and lithium ion and ammonium ion are preferable.

Among the carbon black treated with the acid group described above, the black column spacer formed by using the photosensitive resin composition is selected from the group consisting of a carboxylic acid group, a carboxylic acid group, a sulfonic acid group and a sulfonic acid group in that the relative dielectric constant of the black column spacer is low. Is preferably a carbon black having at least one functional group.

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

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

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

3) A method of reacting an organic compound having a halogen atom and an acidic group and carbon black having a hydroxyl group by the Williamson etherification method.

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

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

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

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

The carbon black into which the acidic group has been introduced may be coated with a resin. When a photosensitive resin composition containing carbon black coated with a resin is used, it is easy to form a black column spacer having excellent light shielding properties and insulation properties and a low surface reflectance. In addition, no adverse influence on the dielectric constant of the black column spacer formed by using the photosensitive resin composition by the coating treatment with the resin occurs particularly. Examples of resins usable for coating carbon black include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyph resin, epoxy resin and alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate and poly Butylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, polyether ether ketone And the like. When the total amount of the carbon black and the resin is 100 parts by weight, the covering amount of the resin to the carbon black is preferably 1 to 30 parts by weight.

Further, the light shielding agent (D) may contain black pigments other than carbon black into which an acidic group is introduced, chromatic pigments such as red, blue, green, yellow, and purple, in addition to carbon black into which an acid group has been introduced, do. Examples of the black pigment other than the carbon black into which the acidic group is introduced include untreated carbon black, perylene pigment, silver tin alloy, titanium black, metal oxides such as copper, iron, manganese, cobalt, chrome, nickel, zinc, Complex oxides, metal sulfides, metal sulfates or metal carbonates. The amount of the dye other than the carbon black to which the acidic group is introduced is preferably 15 parts by weight or less, more preferably 10 parts by weight or less, when the total weight of the (D) light-shielding agent is 100 parts by weight.

The content of the light-shielding agent (D) in the photosensitive resin composition may be appropriately selected within a range not to impair the object of the present invention, and is preferably 5 parts by weight to 50 parts based on 100 parts by weight of the solid content of the photosensitive resin composition . By using the light-shielding agent in such a range, it is easy to suppress the defective exposure and curing defects when the photosensitive resin composition is exposed while the light-shielding property of the black column spacer obtained using the photosensitive resin composition is good.

&Lt; (E) Compound Represented by Formula (1) &gt;

The photosensitive resin composition may contain a compound represented by the following formula (1). When a compound represented by the following formula (1) is blended in the photosensitive resin composition, a black column spacer having particularly excellent adhesion to a substrate can be formed. The compound represented by the following formula (1) generates a base represented by R ¹ -NH-R ² by the action of light. It is considered that the action of improving the adhesion is attributable to the base generated at the time of exposure.

(In the formula (1), R &lt; 1 ^&gt; And R &lt; ² &gt; each independently represent a hydrogen atom or an organic group. Provided that R ¹ and R ² At least one of them represents an organic group. R ¹ And R &lt; ² &gt; may combine with each other to form a cyclic structure or may contain a bond of a hetero atom. R ¹ And R ² are combined to form a cyclic structure, the ring formed may be a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, , A phosphinyl group, a phosphonate group, and an organic group. R ³ represents a single bond or an organic group. R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, A phosphono group, a phosphonate group or an organic group, and Ar is an aromatic group which may have a substituent.

R ¹ Examples of the organic group at R ² include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. 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 linear, branched or cyclic. This organic group is usually monovalent, but may be a divalent or more organic group in the case of forming a cyclic structure.

R ¹ And R &lt; ² &gt; may combine with each other to form a cyclic structure, and may further include a bond of a heteroatom. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and condensed rings may be used.

The bond other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effect of the present invention is not impaired and includes a bond including a hetero atom such as an oxygen atom, a nitrogen atom or a silicon atom . (-N═C (-R) -, -C (═NR) -, R (2), or R (3) may be the same or different and are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Specific examples include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, Represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, and an azo bond.

From the viewpoint of heat resistance, examples of the bond other than the hydrocarbon group in the organic group of R ¹ and R ² include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, -N═C (-R) -, -C (═NR) -: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond or a sulfinyl bond.

Substituents other than the hydrocarbon group in the organic group of R ¹ and R ² are not particularly limited as long as the effect of the present invention is not impaired and examples thereof include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyanato groups, A nitro group, a nitro group, a carboxy group, a carboxyl group, a carboxyl group, a carboxyl group, a carboxyl group, a carboxyl group, a carboxyl group, a carboxyl group, A sulfonyl group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, a hydroxyimino group, an alkyl ether group, an alkenyl ether group, an acyl group, an acyl group, (-NH ₂ , -NHR, -NRR ': R and R' each independently represents a hydrocarbon group), and the like can be given as examples of the alkyl 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 linear, branched and cyclic.

Examples of substituents other than the hydrocarbon groups in the organic group of R ¹ and R ² include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyanato groups, cyanate groups, isocyanate groups, thiocyanate groups, A nitro group, a nitro group, a carboxy group, a carboxylate group, an acyl group, an acyloxy group, a sulfinoxy group, a sulfo group, a sulfo group, a sulfonyl group, a sulfonyl group, , A sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, a hydroxyimino group, an alkyl ether group, an alkenyl ether group, an alkylthioether group, an alkenylthioether group, , An arylthioether group is preferable.

Among them, at least one of R ¹ and R ² is an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms, or is bonded to each other to form a heterocycloalkyl group or a heteroaryl group having 2 to 20 carbon atoms . Examples of the heterocycloalkyl group include a piperidino group and a morpholino group. Examples of the heteroaryl group include an imidazolyl group and a pyrazolyl group.

In the above formula (1), R ³ represents a single bond or an organic group.

Examples of the organic group for R ³ include a group excluding one hydrogen atom from an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or an aralkyl group. The organic group may contain a substituent in the organic group. Examples of the substituent include those exemplified as R ¹ and R ² . The organic group may be either linear or branched.

Among them, R ³ is preferably a single bond, or an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms, in which one hydrogen atom is excluded.

In formula (1), R ⁴ and R ⁵ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, A phosphono group, a phosphono group, a phosphonate group or an organic group.

Examples of the organic group for R ⁴ and R ⁵ include R ¹ And R &lt; ² &gt;. This organic group may contain a hetero atom in the organic group as in the case of R ¹ and R ² . The organic group may be linear, branched or cyclic.

In the formula (1), Ar is an aromatic group which may have a substituent. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Examples of the aromatic group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthrenyl group, a pyridyl group, a pryl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, Group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzimidazolyl group. Among these aromatic groups, a phenyl group and a thienyl group are preferable.

Specific examples of the substituent which the aromatic group may have are the same as the specific examples of R ¹ and R ² .

Among the compounds represented by the formula (1), compounds represented by the following formula (2) which are exposed to generate an imidazole compound represented by the following formula (e1) are preferable.

(Wherein R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, A phosphino group, a phosphinyl group, a phosphonate group or an organic group, and R ⁴ , R ⁵ and Ar are the same as in the formula (1)).

(In the formula ^{(e1), R 6, R} 7 and R ⁸ are the same as in formula (2).)

Examples of the organic group at R ⁶ , R ⁷ and R ⁸ in the formula (2) include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group and an aralkyl group. 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 linear, branched or cyclic. This organic group is usually monovalent, but may be a divalent or higher-valent organic group in the case of forming a cyclic structure.

R ⁶ And R &lt; ⁷ &gt; may combine with each other to form a cyclic structure, or may further include a bond of a heteroatom. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and condensed rings may be used.

The bond included in the organic group of R ⁶ , R ⁷ and R ⁸ is not particularly limited as long as the effect of the present invention is not impaired, and the organic group includes a bond including a hetero atom such as an oxygen atom, a nitrogen atom, . Specific examples of the bond containing a hetero atom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (-N═C (-R) -C (= NR) -: R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond and an azo bond.

Examples of the bond including a hetero atom which the organic group of R ⁶ , R ⁷ and R ⁸ may have include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide (-N═C (-R) -, -C (═NR) -: R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, or a sulfinyl bond is preferable .

When R ⁶ , R ⁷ and R ⁸ are substituents other than the hydrocarbon group, R ⁶ , R ⁷ and R ⁸ are not particularly limited as long as the effect of the present invention is not impaired. Specific examples of R ⁶ , R ⁷ and R ⁸ include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyanato group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, , A silanol group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxylate group, an acyl group, an acyloxy group, a sulfino group, a sulfonate group, An alkyl ether group, an alkenyl ether group, an alkylthioether group, an alkenylthioether group, an arylether group, and an arylthioether 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 linear, branched and cyclic.

As R ⁶ , R ⁷ and R ⁸ , a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms and a halogen atom are preferable, Do.

Among the compounds represented by the formula (2), preferred compounds include compounds represented by the following formula (3).

(Formula (3) ^{of, R 4, R 5, R} 6, R 7 and R ⁸ are the same as in equation ^{(2). R 9, R} 10, R 11, R 12 and R ¹³ each independently represents a hydrogen atom , A halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a sulfino group, a phosphinyl group, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may combine with each other to form a cyclic structure or may contain a heteroatom bond.

Examples of the organic group at R ⁴ and R ⁵ include those exemplified for R ¹ and R ² in the formula (1). This organic group may contain a hetero atom in the organic group as in the case of R ¹ and R ² in the formula (1). The organic group may be linear, branched or cyclic.

Among them, R ⁴ and R ⁵ in the formula (3) each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms , An aryloxyalkyl group having 7 to 16 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, An amide group of 2 to 11 carbon atoms, an alkylthio group of 1 to 10 carbon atoms, an acyl group of 1 to 10 carbon atoms, an ester group of 2 to 11 carbon atoms (-COOR An aryl group having 6 to 20 carbon atoms, an electron-donating group and / or an aryl group having 6 to 20 carbon atoms substituted with an electron-withdrawing group, an electron donating group and / or an electron donating group It is preferable that the aspirating group is a substituted benzyl group, cyano group or methylthio group. More preferably, both of R ⁴ and R ⁵ are a hydrogen atom or R ⁴ is a methyl group, and R ⁵ is a hydrogen atom.

R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, A sulfo group, a sulfone group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonium group or an organic group.

Examples of the organic group in R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ include those exemplified for R ¹ and R ² in formula (1). As in the case of R ¹ and R ² in the formula (1), 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 linear, branched or cyclic.

R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may combine with each other to form a cyclic structure or may contain a heteroatom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and condensed rings may be used. For ^{example, R 9, R 10, R} 11, R 12 and R ¹³ is ^{R 9, R 10, R 11} , R 12 and R ¹³ share a benzene ring atom bonded to combine two or more of them dog A condensed ring such as naphthalene, anthracene, phenanthrene, or indene may be formed.

R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, An aryloxyalkyl group having 7 to 16 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, An ester group, an aryl group having 6 to 20 carbon atoms, an electron donating group and / or an aryl group having 6 to 20 carbon atoms substituted with an electron withdrawing group, a benzyl group substituted with an electron donating group and / A cyano group, a methylthio group, and a nitro group.

In ^{addition, R 9, R 10, R} 11, R 12 and R ¹³ R to combine them at least two ^{9, R 10, R 11,} R 12 and R ¹³ have share the benzene ring atom bonded naphthalene , Anthracene, phenanthrene, indene, or the like is also formed in that the absorption wavelength becomes long.

Among the compounds represented by the above formula (3), compounds represented by the following formula (4) are preferable.

(Formula (4) ^{of, R 4, R 5, R} 6, R 7 and R ⁸ are the same as formula (2) and (3). R ⁹ ~R ¹² is equal to the expression (3). R ¹⁴ is no case represents a hydrogen atom or an organic group. the R ⁹ and R ¹⁰ is a hydroxyl group. R ^9, R ^10, R ¹¹ and R ¹² are optionally, combining two or more of them to form a cyclic structure, heteroatoms May be combined with each other).

Since the compound represented by the formula (4) has a substituent -OR ¹⁴ , it tends to be uniformly dissolved in the thermosetting composition.

In the formula (4), R ¹⁴ is a hydrogen atom or an organic group. When R ¹⁴ is an organic group, organic groups exemplified for R ¹ and R ² in formula (1) may be mentioned. The organic group may contain a hetero atom in the organic group. The organic group may be linear, branched or cyclic. R ¹⁴ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a methyl group.

Specific examples of particularly preferable compounds among the compounds represented by the formula (1) are shown below.

Among the above compounds, the following compounds are more preferable as the compound represented by the formula (1).

In the photosensitive resin composition, the content of the compound represented by the formula (E) (E) is not particularly limited within the range not hindering the object of the present invention. The content of the compound represented by the formula (1) in the photosensitive resin composition is preferably from 0.01 to 50 parts by weight, more preferably from 0.2 to 25 parts by weight, per 100 parts by weight of the photosensitive resin composition.

&Lt; (F) Light absorber &gt;

The photosensitive resin composition may contain 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.

Specifically, cinnamic acid derivatives such as 2-ethylhexyl cinnamate, 2-ethylhexyl paramethoxycinnamate, isopropyl methoxycinnamate, and methoxycinnamic acid isoamyl; 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-dihydroxyanthracene; 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. Among these, cinnamic acid derivatives and naphthalene derivatives are preferred, and cinnamic acid derivatives are particularly preferred. These light absorbents may be used alone or in combination of two or more.

(F) The content of the light absorbent is more preferably 0.5 to 20 parts by weight based on 100 parts by weight of the solid content of the photosensitive resin composition. By keeping 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 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, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono- Propylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; and (poly) alkylene glycol mono Alkyl ethers; (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 acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, acetic acid- n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, , Pyruvic acid-n-propyl, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; Amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide; N, N, N ', N'-tetramethylurea and the like.

Of these, alkylene glycol monoalkyl ether acetates, alkylene glycol monoalkyl ether acetates, the above-mentioned other ethers, alkyl ester of lactic acid 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 concentration of the photosensitive resin composition is 1 to 50% by weight, more preferably 5 to 30% by weight.

<Other ingredients>

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

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

The photosensitive resin composition 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.

By using the above-described photosensitive resin composition, it is possible to form a black column spacer having a low relative dielectric constant. Further, the above-described photosensitive resin composition has good halftone characteristics. Specifically, with the film thickness of the photosensitive resin layer made of a photosensitive resin composition 3㎛, 100mJ / cm film thickness H of the _FT black column spacer is obtained when the exposure is performed with an exposure amount in the ^second configuration by the above-described photosensitive resin composition, 10mJ / the difference ΔH (= H _FT - H _HT ) of the film thickness H _HT of the black column spacer obtained when exposure is performed at an exposure amount of 5,000 Å / cm ² can be 5000 Å or more.

«Black column spacer, display device, method of forming black column spacer»

The black column spacer was the same as the conventional black column spacer except that it was formed from the photosensitive resin composition described above. The display device is the same as that of the conventional display device except that it has a black column spacer formed from the photosensitive resin composition described above. Hereinafter, only the method of forming the black column spacer will be described.

The method of forming a black column spacer according to the present invention includes a coating step of coating a photosensitive resin composition on a substrate to form a photosensitive resin layer, an exposure step of exposing the photosensitive resin layer to a predetermined black column spacer pattern, And developing the photosensitive resin layer to form a pattern of the black column spacer.

First, in a coating process, 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, a spinner (rotary coating device), or a curtain flow coater is used to form a black column spacer Is applied on the photosensitive resin composition, and if necessary, the solvent is removed by drying to form a photosensitive resin layer.

Then, in the exposure step, an active energy ray such as ultraviolet rays, excimer laser light or the like is irradiated to the photosensitive resin layer through a negative mask to partially expose the photosensitive resin layer according to the pattern of the black column spacer do. 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 differs depending on the composition of the photosensitive resin composition, but is preferably, for example, about 10 to 600 mJ / cm ² .

When the substrate is formed on a substrate such as a TFT substrate, it may be necessary to form a black column spacer on the element or at a position facing the element of the substrate mating with the substrate on which the element is formed. In this 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, 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.

Then, 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 developing solution 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 subjected to post-baking and cured by heating. Post baking is preferably performed at 150 to 250 캜 for 15 to 60 minutes.

The black column spacer formed using the photosensitive resin composition described above has a low relative dielectric constant and a high OD value. Specifically, the relative dielectric constant of such a black column spacer at 1 kHz is preferably 6 or less, and more preferably 2 to 5.5. The OD value per 1 탆 of the thickness of the black column spacer is preferably 1.0 or more, more preferably 1.0 to 4.5.

[Example]

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

In Examples and Comparative Examples, the following CB-A, CB-B, CB-C and CB-D were used as light shielding agents. CB-D was obtained by coating 100 parts by weight of CB-C with 10 parts by weight of an epoxy group-containing compound (weight average molecular weight 10,000). The light shielding agent was used as a carbon black dispersion. A method for producing a carbon black dispersion is described below as Preparation Example 3. [

CB-A: Carbon black into which the benzenesulfonic acid group obtained in Preparation Example 1 was introduced.

CB-B: Carbon black into which the benzene carboxylic acid group obtained in Preparation Example 2 was introduced.

CB-C: Carbon black (Regal 250R, made by Cabot) which has not undergone acidic group introduction treatment,

CB-D: Carbon black coated with resin.

In the examples and comparative examples, the resin (A-1) obtained in the following Preparation example 4 was used as the alkali-soluble resin.

In the Examples and Comparative Examples, dipentaerythritol hexaacrylate was used as the photopolymerizable monomer.

In Examples and Comparative Examples, PI-A and PI-B described below were used as a photopolymerization initiator.

PI-A: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- : Manufactured by BASF)

PI-B: Compound of the formula

In Examples and Comparative Examples, a mixed solvent composed of 3-methoxybutyl acetate (60% by weight) and propylene glycol monomethyl ether acetate (40% by weight) was used as the organic solvent.

(Preparation Example 1: Preparation of CB-A)

550 g of carbon black (Regal 250R, manufactured by Cabot), 31.5 g of sulfanilic acid and 1000 g of ion-exchanged water were added to a reaction vessel equipped with a jacket set at a jacket temperature of 60 캜 and a stirring device. A solution prepared by dissolving 12.6 g of sodium nitrite in 100 g of deionized water was added to a brow mixer and the mixture was stirred for 2 hours at 60 ° C and 50 rpm in a mixer to perform a diazo coupling reaction. After stirring, the contents of the mixer were cooled to room temperature. Subsequently, the carbon black contained in the contents of the mixer was purified by a diaphotration method using deionized water. From the washing water, benzenesulfonic acids derived from sulfanilic acid were not detected, and it was found that a benzenesulfonic acid group was introduced into the carbon black by the diazo coupling reaction. The purified carbon black was dried overnight at 75 캜 and then pulverized to obtain a carbon black (CB-A) into which a benzenesulfonic acid group was introduced.

(Preparation Example 2: Preparation of CB-B)

Carbon black (CB-B) having a benzene carboxylic acid group introduced therein was obtained in the same manner as in Preparation Example 1, except that 31.5 g of sulfanilic acid was changed to 24.9 g of 4-aminobenzoic acid.

(Preparation Example 3: preparation of dispersion of carbon black)

Carbon black dispersions were prepared by using CB-A, CB-B and CB-C described above as carbon black according to the following formulation.

15 g of carbon black, 7.5 g of a dispersant (BYK-167, manufactured by Big Chem Co., Ltd.) and 50 g of 3-methoxybutyl acetate were uniformly mixed, and carbon black was dispersed in 3-methoxybutyl acetate. Thereafter, the mixture was diluted with 3-methoxybutyl acetate to have a solid content concentration of 30% by weight to obtain a carbon black dispersion.

(Preparation Example 4: preparation of resin (A-1)) [

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 were added to a 500 ml four- And heated to 90 to 100 캜 while blowing air at a rate of 25 ml / min. Subsequently, the solution was gradually elevated to a cloudy state and heated to 120 DEG C to be completely dissolved. At this time, the solution became gradually transparent dots, but stirring was continued. During this period, the acid value was measured, and heating and stirring were continued until the concentration was less than 1.0 mg KOH / g. It took 12 hours until the acid value reached the target value. Then, the mixture was cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate represented by the following formula (a-4) which was colorless and transparent and was in a solid state.

Subsequently, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene-type epoxy acrylate thus obtained, and then 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and slowly heated The reaction was carried out 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 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).

[Examples 1 to 8 and Comparative Examples 1 to 5]

50 parts by weight of an alkali-soluble resin, 35 parts by weight of a photopolymerizable monomer, 15 parts by weight of a photopolymerization initiator (PI-A), and a carbon black dispersion containing carbon black of the kind and amount described in Table 1 were uniformly mixed. The alkali-soluble resin was used in the form of a 3-methoxybutyl acetate solution having a solid concentration of 55% by weight. The obtained mixed solution was diluted with a mixed solvent composed of 3-methoxybutyl acetate (60% by weight) and propylene glycol monomethyl ether acetate (40% by weight) so as to have a solid concentration of 15% by weight, Followed by filtration through a membrane filter of 5 mu m to obtain a photosensitive resin composition. The OD values per 1 mu m of the light-shielding film, the relative dielectric constant of the light-shielding film, and the halftone characteristics of the photosensitive resin composition were evaluated by the following methods using the photosensitive resin compositions of the obtained examples and comparative examples. The results of these evaluations are shown in Table 1.

[Evaluation of OD value]

The OD values per 1 mu m of the thickness of the light-shielding film formed using the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 5 were evaluated by the following method.

First, a photosensitive resin composition was spin-coated on a glass substrate (10 cm x 10 cm). After spin application, the glass substrate was heated at 90 DEG C for 120 seconds. Subsequently, the photosensitive resin layer was exposed using a Miller projection aligner (TME-150RTO, manufactured by Topcon Co., Ltd.) under the conditions of an exposure dose of 100 mJ / cm ² and a gap of 200 탆. The exposed photosensitive resin layer was post-baked at 230 캜 for 30 minutes to form a light-shielding film. The film thickness of the formed light-shielding film was 1.0 탆. The OD value of the formed light-shielding film was measured using a transmittance meter (D-200 II, manufactured by Gretec Macbeth). The larger the OD value, the better the light shielding property.

[Evaluation of relative dielectric constant]

The relative dielectric constant of the light-shielding film formed using the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 5 was evaluated according to the following method.

First, a photosensitive resin composition was spin-coated on the surface of a 6-inch silicon wafer substrate (manufactured by Shin-Etsu Chemical Co., Ltd.). After the spin coating, the silicon wafer substrate was heated at 90 DEG C for 120 seconds. Subsequently, the photosensitive resin layer was exposed using a Miller projection aligner (TME-150RTO, manufactured by Topcon Co., Ltd.) under the conditions of an exposure dose of 100 mJ / cm ² and a gap of 200 탆. The exposed photosensitive resin layer was post-baked at 230 캜 for 30 minutes to form a light-shielding film. The thickness of the formed light-shielding film was 1.0 탆. The relative dielectric constant of the formed light-shielding film at 1 kHz was measured using a dielectric constant measuring device (SSM495, manufactured by SSM Japan). A case where the relative dielectric constant was 5.5 or less was evaluated as &amp; cir &amp; and a case where the relative dielectric constant exceeded 5.5 was evaluated as x.

[Halftone Characteristic Evaluation]

The halftone characteristics of the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 5 were evaluated by the following method.

First, a photosensitive resin composition was spin-coated on a glass substrate (10 cm x 10 cm). After spin coating, the glass substrate was heated at 90 占 폚 for 120 seconds to form a photosensitive resin layer having a film thickness of 3.0 占 퐉. Then, it was exposed to mirror projection aligner (TME-150RTO, Ltd. Saratov cone agent) in the photosensitive exposure dose 10mJ / cm ² and light exposure 100mJ / cm ² by using a resin layer. The exposed photosensitive resin layer was spray-developed for 60 seconds with a KOH aqueous solution having a concentration of 0.04% by weight at 26 占 폚. The developed photosensitive resin layer was post-baked at 230 캜 for 30 minutes to form a black column spacer. Black columns film difference △ H with a thickness H _HT of the spacer film is formed to a thickness H _FT and the exposure value 10mJ / cm ² of black column spacer formed in the light exposure 100mJ / cm ² - halftone characteristic obtaining a (= H _FT H _HT) of Respectively.

From the photosensitive resin composition of the comparative example comprising the photosensitive resin composition of the example including the carbon black treated with the introduction of the acid group as the light shielding agent and the carbon black not subjected to the treatment of introducing the acid group from Table 1, Tone characteristics and the OD value of the formed black column spacer.

In addition, the black column spacers formed using the photosensitive resin composition of the comparative example including the carbon black not subjected to the treatment for introducing the acid group from Table 1 show that the relative dielectric constant rapidly increases with the increase of the content of carbon black , And that the black column spacer formed using the photosensitive resin composition of the example including carbon black treated with the introduction of an acid group as a light shielding agent can maintain a low dielectric constant of 5.5 or less even when increasing carbon black.

From the comparison of the comparative examples 6 to 9 and the comparative examples 1 to 5, it can be understood that when resin-coated carbon black is used as the light shielding agent, carbon black which is not coated with resin is used as the light shielding agent, The rise of the relative dielectric constant of the black column spacer formed by the above-described method can be suppressed only slightly.

[Examples 9 to 11]

A photosensitive resin composition of Examples 9 and 10 was prepared in the same manner as in Example 4 except that the photopolymerization initiator was changed from 15 parts by weight of PI-A to a combination of PI-A and PI-B in the amounts shown in Table 2. [ A photosensitive resin composition of Example 11 was prepared in the same manner as in Example 4 except that the photopolymerization initiator was changed from 15 parts by weight of PI-A to 15 parts by weight of PI-B. The OD value per 1 mu m of the light-shielding film, the relative dielectric constant of the light-shielding film, and the halftone property of the photosensitive resin composition were evaluated for the obtained photosensitive resin composition. The evaluation results are shown in Table 2.

From Table 2, it was found that the halftone property of the photosensitive resin composition was particularly excellent when the photosensitive resin composition contained the compound represented by the above formula (c-1). From Table 2, it was found that the halftone characteristics were better in the photosensitive resin composition as the content of the compound represented by the formula (c-1) in the photopolymerization initiator was larger.

[Example 12]

A photosensitive resin composition of Example 12 was prepared in the same manner as in Example 4, except that 5 parts by weight of the compound represented by the following formula was added to the photosensitive resin composition as the compound represented by the formula (1). The adhesion of the formed black column spacer to the substrate was evaluated in addition to the OD value per 1 탆 of the light-shielding film, the relative dielectric constant of the light-shielding film, and the halftone property of the photosensitive resin composition. The adhesion of the black column spacer to the substrate was evaluated according to the following method. Evaluation of the adhesion of the formed black column spacer to the substrate was also performed on the photosensitive resin composition of Example 4. The evaluation results are shown in Table 3.

[Evaluation of adhesion]

The adhesion of the black column spacer formed using the photosensitive resin composition to the substrate was evaluated according to the following method.

First, a photosensitive resin composition was spin-coated on a glass substrate (10 cm x 10 cm). After spin coating, the glass substrate was heated at 90 占 폚 for 120 seconds to form a photosensitive resin layer having a film thickness of 3.0 占 퐉. Subsequently, the photosensitive resin layer was exposed using a Miller projection aligner (TME-150RTO, manufactured by Topcon Co., Ltd.) with an exposure dose of 50 mJ / cm ² via a negative mask. Then, the exposed photosensitive resin layer was spray-developed at 25 캜 using a KOH aqueous solution having a concentration of 0.04% by weight. The development time was set at about 1.5 times the BP, based on the time (BP: break point) until the unexposed portion was completely dissolved. Thereafter, the developed photosensitive resin layer was post-baked at 230 캜 for 20 minutes to form a black column spacer. The minimum size of the mask capable of forming the black column spacer on the glass substrate was examined according to the above procedure. The better the adhesion of the formed black column spacer, the smaller the minimum value of the mask. The case where the minimum dimension of the mask was 10 占 퐉 or less with respect to the adhesion property was evaluated as?, And the case where the size was more than 10 占 퐉 and 40 占 퐉 or less was evaluated as?

From Table 3, it was found that when the photosensitive resin composition contains the compound represented by the above-mentioned formula (1), it is possible to form a black column spacer having particularly excellent adhesion to the substrate.

[Examples 13 to 17 and Comparative Example 10]

The photosensitive resin compositions of Examples 13 to 17 were obtained in the same manner as in Example 3 except that the amount of the photopolymerizable monomer was changed from 35 parts by weight to the amount shown in Table 4. [

The same procedure as in Comparative Example 1 was carried out except that the content of the carbon black in the photosensitive resin composition was changed from 5 parts by weight to 12.5 parts by weight and that the amount of the photopolymerizable monomer was changed from 35 parts by weight to 50 parts by weight, To obtain a resin composition.

When the photosensitive resin composition of each of Examples 13 to 17 and Comparative Example 10 contains 100 parts by weight of the content of the alkali-soluble resin, the content B of the photopolymerizable monomer, and the content C of the photopolymerization initiator in the photopolymerizable composition The number of parts by weight D of the monomers is shown in Table 5.

The OD value per 1 mu m of the light-shielding film, the relative dielectric constant of the light-shielding film, the halftone property of the photosensitive resin composition, and the adhesion of the formed black column spacer to the substrate were evaluated for the obtained photosensitive resin composition. The results of these evaluations are shown in Table 4.

According to Examples 13 to 17, when the content of the alkali-soluble resin, the content of the photopolymerizable monomer, and the content of the photopolymerization initiator is 100 parts by weight, the content of the photopolymerizable monomer in the photosensitive resin composition is smaller, It was found that the adhesion of the column spacer to the substrate was good.

Claims (11)

(A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a light-
The photosensitive resin composition for forming a black column spacer as described in (D) above, wherein the light-shielding agent contains carbon black to which an acidic group has been introduced. The method according to claim 1,
Wherein the carbon black has at least one functional group selected from the group consisting of a carboxylic acid group, a carboxylic acid group, a sulfonic acid group and a sulfonic acid salt group. The method according to claim 1 or 2,
The content of the photopolymerizable monomer (B) is preferably 5 to 50 parts by weight per 100 parts by weight of the total amount of the content of the alkali-soluble resin (A), the content of the photopolymerizable monomer (B), and the content of the photopolymerization initiator (C) A photosensitive resin composition for forming a black column spacer. The method according to any one of claims 1 to 3,
Wherein the photopolymerization initiator (C) comprises an oxime ester photopolymerization initiator. The method according to any one of claims 1 to 4,
Wherein the content of the carbon black is 1 to 30 parts by weight based on 100 parts by weight of the total amount of the content of the alkali-soluble resin (A), the content of the photopolymerizable monomer (B), and the content of the photopolymerization initiator (C) Sensitive resin composition. The method according to any one of claims 1 to 5,
The photosensitive resin composition for forming a black column spacer, wherein the alkali-soluble resin (A) comprises a resin having a cardo structure. The method according to any one of claims 1 to 6,
And the black column spacer can 3㎛ photosensitive film having a thickness made up of a photosensitive resin composition for forming the resin layer, 100mJ / cm film thickness H of the _FT black column spacer is obtained when the exposure is performed with an exposure amount of the ^second exposure value by the exposure of 10mJ / cm ² And the film thickness H _HT of the black column spacer obtained when the film thickness is H (= H _FT - H _HT ) of 5000 angstroms or more. A black column spacer formed from the photosensitive resin composition for forming a black column spacer according to any one of claims 1 to 7. The method of claim 8,
A black column spacer having an OD value per 1 탆 of film thickness of 1.0 or more and a dielectric constant at 1 kHz of 6 or less. A display device comprising the black column spacer according to claim 8 or 9. A process for producing a black column spacer, comprising the steps of: applying a photosensitive resin composition for forming a black column spacer according to any one of claims 1 to 7 onto 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.