KR20150077331A - Photosensitive resin composition for black column spacer - Google Patents

Abstract

The present invention provides a photosensitive resin composition for a black column spacer that can form a black column spacer having an uniform height when being applied on a substrate and can also form a black column spacer having an enough height difference in a halftone part and having a full-tone part as a photosensitive resin layer is exposed to light by interposing a halftone mask; a black column spacer formed from the same photosensitive resin composition; a display device having the same black column spacer; and a method for forming a black column spacer using the same photosensitive resin composition. The photosensitive resin composition for a black column spacer includes an alkali soluble resin, a photo polymerizable compound, a photo polymerization initiator, a light-shielding agent, and a solvent including a certain amount of a low boiling point solvent (L) having a boiling point of 170°C under atmospheric pressure and a certain amount of a high boiling point solvent (H) having a boiling point of 180°C under atmospheric pressure.

Description

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

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

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

Conventionally, in order to form a spacer, a method of dispersing bead particles as spacers on the entire surface of a substrate has been adopted. However, in this method, it is difficult to form 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, since black column spacers are required to have high dimensional accuracy particularly with respect to height, when the photosensitive resin composition described in Patent Document 1 is used, it is difficult to form a black column spacer having a uniform height depending on the composition of the photosensitive resin composition . This is because it is difficult to form a photosensitive resin layer having a uniform thickness when the photosensitive resin composition described in Patent Document 1 is applied on a substrate.

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, it is preferable to perform exposure through the half-tone mask because the black column spacer having different heights can be formed at one time by changing the exposure amount depending on the place where the black column spacer is formed.

However, the inventors of the present invention have found that it is difficult to form a black column spacer having a sufficient difference in height even when exposure is performed through a halftone mask in the photosensitive resin composition described in Patent Document 1. The characteristic for forming a black column spacer having a sufficient difference in height by performing exposure through a halftone mask is also referred to as " halftone characteristic ".

SUMMARY OF THE INVENTION It is an object of the present invention to provide a black column spacer having a uniform height and a black column spacer A black column spacer formed from the photosensitive resin composition; a display device including the black column spacer; and a method of forming a black column spacer using the photosensitive resin composition .

DISCLOSURE OF THE INVENTION The present inventors have conducted diligent studies to achieve the above object. As a result, it has been found that a photosensitive resin composition for a black column spacer containing an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a photopolymerization initiator, a light-shielding agent and a solvent, wherein (L) a low boiling point solvent having a boiling point of less than 170 占 폚 at atmospheric pressure, And (H) high-boiling point solvent having a specific boiling point of not less than < RTI ID = 0.0 > 100 C < / RTI > Specifically, the present invention provides the following.

A first aspect of the present invention relates to a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a light-

(L) a low boiling point solvent having a boiling point of less than 170 占 폚 at atmospheric pressure and (H) a high boiling point solvent having a boiling point of 180 占 폚 or higher at atmospheric pressure,

(S) the content of the low boiling point solvent (L) in the solvent is 30 to 99 wt%

And the content of the (H) high boiling point solvent in the (S) solvent is 1 to 15% by weight.

A second aspect of the present invention is a black column spacer made of the photosensitive resin composition for 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.

A fourth aspect of the present invention is a method for manufacturing a black column spacer comprising the steps of forming a photosensitive resin layer by coating a photosensitive resin composition for a black column spacer according to the first aspect on a substrate,

A step of exposing the photosensitive resin layer according to a pattern of a predetermined spacer,

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

According to the present invention, it is possible to form a black column spacer having a uniform height when coated on a substrate, and to expose a photosensitive resin layer through a halftone mask to form a black column spacer having a sufficient difference in height in the full- A black column spacer formed from the photosensitive resin composition; a display device including the black column spacer; and a method of forming a black column spacer using the photosensitive resin composition. have.

«Photosensitive resin composition for black column spacer»

The photosensitive resin composition for a black column spacer according to the present invention (hereinafter simply referred to as "photosensitive resin composition") contains an alkali soluble resin, a photopolymerizable compound, a photopolymerization initiator, a light shielding agent and a solvent. As the solvent, a solvent containing a specific amount of (L) a low-boiling solvent having a boiling point of less than 170 ° C at atmospheric pressure and (H) a high boiling point solvent having a boiling point of 180 ° C or higher at atmospheric pressure is used. Hereinafter, each component contained in the photosensitive resin composition will be described.

<(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. Examples of suitable resins as the (A) alkali-soluble resin include (A1) polymers which are resins having at least one structure represented by the following formulas (i) to (iii).

Among the polymers (A1), a resin having a structure represented by the formula (i) is preferable in that the black column spacer formed by using the photosensitive resin composition is excellent in heat resistance. The structure represented by the formula (i) is generally referred to as a cardo structure, and the resin having the structure represented by the formula (i) is generally referred to as a cardo resin.

As the polymer (A1), 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-3-1), (a-3-2) or (a-3-3).

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.

(A1) The weight average molecular weight (Mw: measured value by gel permeation chromatography (GPC) in terms of styrene conversion) of the polymer is preferably 1000 to 40000, more preferably 2000 to 30,000 Do. 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 unsaturated carboxylic acid (a1) and a constituent unit having a polymerizable moiety with a photopolymerizable compound (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, A resin containing a copolymer having at least a constituent unit having a polymerizable portion with a photopolymerizable compound can be 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.

(B) a constituent unit having a polymerizable moiety with the photopolymerizable compound (B) preferably has an ethylenic unsaturated group as a polymerizable moiety with the photopolymerizable compound (B). 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) the constituent units derived from 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 compound (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 constituent units derived from unsaturated carboxylic acid (a1) is preferably 1 to 50% by weight, and more preferably 5 to 45% by weight. In the copolymer (A4), the proportion of the 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 ratio of the constituent unit having a polymerizable moiety to the photopolymerizable compound (B) is 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 photosensitive resin composition preferably contains at least one acrylic resin selected from the above-mentioned (A1) polymer as the alkali-soluble resin (A), the (A2) copolymer, the (A3) copolymer and the (A4) . The acrylic resin is a resin containing a constitutional unit derived from (meth) acrylic acid and a constitutional unit derived from a (meth) acrylate, wherein the content of the constituent unit derived from (meth) acrylic acid in the resin and the content of The total content of the constituent units derived from the ester is 60% by weight or more, preferably 70% by weight or more, and more preferably 80% by weight or more. The acrylic resin may contain a constitutional unit derived from (meth) acrylic acid and a constitutional unit other than the constitutional unit derived from the (meth) acrylate ester. The constituent unit derived from (meth) acrylic acid and the constituent unit other than the constituent unit derived from the (meth) acrylic acid ester is not particularly limited as long as it is a constituent unit derived from a monomer copolymerizable with (meth) acrylic acid and (meth) acrylic acid ester . Examples of the structural unit other than the structural unit derived from (meth) acrylic acid and the structural unit derived from the (meth) acrylic acid ester include the above-mentioned (meth) acrylamides, acrylic compounds, vinyl ethers, styrenes and vinyl esters And a structural unit derived from a monomer selected from the group consisting of a hydroxyl group and a hydroxyl group.

(X) to the content (X) of the polymer (A1) with respect to the content (Y) of the acrylic resin when the photosensitive resin composition contains the aforementioned (A1) polymer and the acrylic resin as the acrylic- Y) is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, and most preferably 20/80 to 80/20. When the photosensitive resin composition contains (A) a polymer (A1) polymer and an acrylic resin as the alkali-soluble resin (A) at such a ratio, the uniformity of the film thickness of the photosensitive resin layer formed using the photosensitive resin composition, The balance of properties is particularly good.

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. In the case where the total amount of the alkali-soluble resin (A), the alkali-soluble resin content, the content of the photopolymerizable compound (B) 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 compound (B) in the composition is 5 to 50 parts by weight.

&Lt; (B) Photopolymerizable compound &gt;

(B) Photopolymerizable compounds include monofunctional compounds and polyfunctional compounds.

Examples of monofunctional compounds 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 compounds may be used alone or in combination of two or more.

Examples of the polyfunctional compound 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 compound Or triacryl amide, and the like. These polyfunctional compounds may be used alone or in combination of two or more.

The content of the photopolymerizable compound (B) is preferably from 1 to 40% by weight, more preferably from 5 to 30% by weight, based on the solid content of the photosensitive resin composition. When the concentration is in the above range, balance of sensitivity, developability and resolution tends to be easily obtained.

<(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 isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, an n-octyloxycarbonyl group, an isooctyloxycarbonyl group , a sec-octyloxycarbonyl group, a tert-octyloxycarbonyl group, an n-nonyloxycarbonyl group, an isononyloxycarbonyl group, a n-decyloxycarbonyl group and an isodecyloxycarbonyl group.

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 one or more N, S, O, or a heterocyclyl group in which the monocyclic ring or the benzene ring is condensed with such monocyclic ring. 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, has high solubility in solvents, and the like, and has a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms An alkoxy group 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 coupling can (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 that 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 20 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 with 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, the binding position of R ^c4 is preferably in the para position relative to the number bonded to the phenyl group of R ^c4 is bonded with 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. It is easy to prepare a photosensitive resin composition having good coating properties and curability by setting to the above-mentioned range.

<(D) Shading agent>

As the light shielding agent (D), those conventionally compounded in the photosensitive resin composition can be used without particular limitation. As the light-shielding agent, it is preferable to use a black pigment. Examples of the black pigment include metal oxides such as carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium and silver, complex oxides, metal sulfides, metal sulfates, metal carbonates And the like. Among these, it is preferable to use carbon black having high light shielding properties.

As carbon black, known carbon black such as channel black, furnace black, thermal black and lamp black can be used, but it is preferable to use channel black having excellent light shielding properties.

It is also preferable to use carbon black to which an acidic group is introduced as the carbon black. When carbon black treated with an acidic group is added to the photosensitive resin as the light shielding agent (D), it is easy to form a black column spacer having a low relative dielectric constant by using the photosensitive resin composition.

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.

When the light shielding agent is carbon black, carbon black coated with a resin may be used. 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. 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.

The coating treatment with a resin may be carried out on a carbon black to which an acidic group-introduced treatment is applied. There is no particular adverse effect caused by the coating treatment by the resin with respect to the dielectric constant of the black column spacer formed by using the photosensitive resin composition containing the carbon black subjected to the treatment of introducing the acidic group.

As the light shielding agent (D), a mixture of a plurality of black pigments may be used for the purpose of color tone adjustment, or a mixture of chromatic pigments such as red, blue, green, yellow and purple may be used.

In order to uniformly disperse (D) the light-shielding agent in the photosensitive resin composition, a dispersing agent may be further used. As such a dispersing agent, it is preferable to use a polymeric dispersant of polyethylene imide, urethane resin or acrylic resin. Particularly when carbon black is used as the light shielding agent (D), it is preferable to use an acrylic resin-based dispersant as a dispersant.

In the photosensitive resin composition, the content of the light-shielding agent (D) may be appropriately selected within a range that does not 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.

The content of the light-shielding agent (D) in the photosensitive resin composition is preferably adjusted so that the OD value per 1 m of the thickness of the black matrix is 4 or more. When the OD value per 1 m of the film thickness in the black matrix is 4 or more, sufficient display contrast can be obtained when the black matrix is used for a black matrix of a liquid crystal display.

<(S) Solvent>

The photosensitive resin composition according to the present invention contains a (S) solvent for dilution. (S) solvent essentially comprises (L) a low boiling point solvent having a boiling point of less than 170 DEG C at atmospheric pressure and (H) a high boiling point solvent having a boiling point of 180 DEG C or higher at atmospheric pressure. (L) the content of the low boiling point solvent in the (S) solvent is 30 to 99 wt%, and the content of the (H) high boiling point solvent is 1 to 15 wt%. (S) solvent may include a medium boiling point solvent having a boiling point of 170 ° C or higher and lower than 180 ° C at atmospheric pressure.

The content of the (H) high boiling point solvent in the (S) solvent is preferably from 1 to 10% by weight, more preferably from 1 to 8% by weight, and particularly preferably from 1 to 5% by weight. The content of the (L) low-boiling solvent in the (S) solvent is preferably 40 to 99 wt%, more preferably 45 to 99 wt%, particularly preferably 50 to 99 wt%, most preferably 55 to 99 wt% Do.

The boiling point of the high boiling point (H) solvent under atmospheric pressure is not particularly limited as long as it is 180 占 폚 or higher, but it is preferably 180 占 폚 or higher and 300 占 폚 or lower. When the photosensitive resin composition is used to form the photosensitive resin layer by containing the (H) high boiling point solvent having a boiling point within this range in the above-mentioned predetermined amount (S) solvent, (S) is volatilized at a proper rate, The difference in the film thickness of the ground layer is reduced.

Specific examples of the (H) high boiling point solvent include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, N-butyl ether acetate, 1,6-hexanediol diacetate, epsilon -caprolactone, 1, 2-butanediol diacetate, diethylene glycol mono-n- 3-butylene glycol diacetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol methyl-n-butyl ether, As it may be a lactone, dipropylene glycol methyl -n- propyl ether, and propylene glycol diacetate.

Among the above-mentioned (H) high boiling point solvents, 1,4-butanediol diacetate, diethylene glycol mono-n-butyl ether acetate, 1 Diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol methyl-n-butyl ether,? -Caprolactone,? -Caprolactone, 1,3-butylene glycol diacetate, Butyrolactone, dipropylene glycol methyl-n-propyl ether and propylene glycol diacetate are preferable. The (S) solvent may contain two or more of these (H) high boiling point solvents in combination.

(L) The boiling point of the low boiling point solvent under atmospheric pressure is not particularly limited as long as it is less than 170 占 폚, but it is preferably 100 占 폚 or more and less than 170 占 폚. When the photosensitive resin composition is applied to the substrate to contain the low boiling point solvent having a boiling point within the above range in the predetermined amount (S) solvent, the solvent of the (S) solvent volatilizes at a proper rate, The residual amount of the (S) solvent in the resin layer can be reduced.

When the photosensitive resin layer containing a large amount of (S) solvent is exposed through a halftone mask, the curing of the photosensitive resin layer progresses excessively quickly due to the action of the (S) solvent, The height of the column spacer is substantially unchanged in the full-tone portion and the half-tone portion. However, when the low-boiling point solvent (L) is contained in the predetermined amount (S) solvent, the residual amount of the (S) solvent in the photosensitive resin layer can be reduced, whereby the photosensitive resin layer The difference in height between the full-tone part and the half-tone part can be sufficiently increased with respect to the black column spacer obtained by exposure after development.

Specific examples of the low boiling point solvent (L) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono- Propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, tetrahydrofuran, methyl ethyl ketone, 2-heptanone, 3-heptanone, ethyl acetate, N-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, N-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, propylene glycol monomethyl ether acetate Tetra, cyclohexanone, 3-methoxybutanol and cyclopentanone.

Of the above-mentioned (L) low-boiling point solvents, propylene glycol monomethyl ether acetate, cyclohexanone, 3- (3-hydroxyphenyl) propane, Methoxybutanol and cyclopentanone are preferred. (S) solvent may contain two or more of these (L) low-boiling solvents.

(S) solvent may contain a medium boiling point solvent having a boiling point of 170 占 폚 or more and less than 180 占 폚 under atmospheric pressure in addition to the (H) high boiling point solvent and (L) low boiling point solvent. The kind of the (M) middle boiling point solvent is not particularly limited as long as it can dissolve the components contained in the photosensitive resin composition. Preferred examples of the (M) medium boiling point solvent include 3-methoxybutyl acetate, N, N, N ', N'-tetramethylurea, dipropylene glycol dimethyl ether and cyclohexanol acetate. (S) solvent may contain two or more of these (M) medium boiling point solvents in combination.

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.

«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 varies 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.

[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.

[Examples 1 to 29 and Comparative Examples 1 to 11]

20 parts by weight of an alkali-soluble resin, 20 parts by weight of a photopolymerizable compound (dipentaerythritol hexaacrylate), 10 parts by weight of a photopolymerization initiator (OXE-02, manufactured by BASF), and 50 parts by weight of a carbon dispersion, Were dispersed in a solvent having the composition described in Tables 1 to 4 so as to be in a weight%. The obtained dispersion was uniformly dissolved by stirring in an agitator for 1 hour. The obtained solution was filtered with a membrane filter having an opening diameter of 5 탆 to obtain the photosensitive resin compositions of the respective Examples and Comparative Examples.

In Examples 1 to 29 and Comparative Examples 1 to 11, the cardo resin (A-1) obtained in the following Preparation Example 1 and an acrylic resin of the following formula were used as the alkali-soluble resin. The weight average molecular weight of the acrylic resin of the following formula is 8,000. The number in the lower right corner of each structural unit in the following formula is the molar ratio of each structural unit in all structural units constituting the acrylic resin. In the examples 1 to 29 and the comparative examples 1 to 11, the cardo resin and the acrylic resin were compounded in the photosensitive resin composition so that the mass ratio of both (cardo resin: acrylic resin) was 70:30.

[Preparation Example 1]

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

First, 235 g of a bisphenol fluorene 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 prepared in 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.

Further, the cardo resin (A-1) corresponds to the resin represented by the above formula (a-1).

In Examples 1 to 29 and Comparative Examples 1 to 11, the carbon dispersion had a solid concentration of 30% by weight, a content of carbon black of 20% by weight, a content of dispersant of 10% by weight, Lt; / RTI &gt; butylacetate was used.

In Examples 1 to 29 and Comparative Examples 1 to 11, the following compounds were used as the (L) low boiling point solvent.

PM: Propylene glycol monomethyl ether acetate

AN: cyclohexanone

CP: cyclopentanone

MB: 3-methoxybutanol

(M) As the zero point for the middle boiling point, the following were used.

MA: 3-methoxybutylacetate

TMU: N, N, N ', N'-tetramethylurea

DMM: dipropylene glycol dimethyl ether

CHXA: Cyclohexanol acetate

(H) As the high boiling point zero, the following were used.

BDDA: 1,4-butanediol diacetate

BDGAC: diethylene glycol monobutyl ether acetate

HDDA: 1,6-hexanediol diacetate

ECL:? -Caprolactone

BGDA: 1,3-butylene glycol diacetate

EDGAC: diethylene glycol monoethyl ether acetate

DPMA: dipropylene glycol methyl ether acetate

MBGD: diethylene glycol methyl butyl ether

GBL:? -Butyrolactone

DPMNP: dipropylene glycol methyl-n-propyl ether

PGDA: Propylene glycol diacetate

The halftone characteristics of the photosensitive resin compositions of each of the examples and comparative examples were evaluated by the following methods. Further, as the evaluation corresponding to the uniformity of the height of the black column spacer, the photosensitive resin compositions of each of the examples and the comparative examples were subjected to exposure and development of a photosensitive resin layer formed using the photosensitive resin composition according to the following method, The difference in film thickness was evaluated.

[Halftone Characteristic Evaluation]

The halftone characteristics of the photosensitive resin compositions of the Examples and Comparative Examples were evaluated according to the following methods.

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 100 DEG C for 120 seconds to form a photosensitive resin layer having a film thickness of 3.0 mu m. 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. Tables 1 to 4 show the values of? H (?) With respect to the photosensitive resin compositions of the examples and comparative examples. The case where the value of DELTA H is 2000 angstroms or more is good.

[Evaluation of Difference in Film Thickness of Cured Film]

The photosensitive resin composition was spin-coated on a glass substrate (10 cm x 10 cm). After spin application, the glass substrate was heated at 100 DEG C for 120 seconds to form a photosensitive resin layer having a film thickness of 3.0 mu m. Subsequently, the photosensitive resin layer was exposed with an exposure dose of 100 mJ / cm ² using Miller Projection aligner (TME-150RTO, manufactured by Topcon Co., Ltd.). The exposed photosensitive resin layer was spray-developed for 120 seconds in a KOH aqueous solution having a concentration of 0.04% by weight at 26 캜. The developed photosensitive resin layer was post-baked at 230 캜 for 20 minutes to form a cured film. The difference in film thickness of the cured film formed was evaluated using a stylized film thickness measuring apparatus (Dektak). More specifically, the film thickness was measured at five points in the cured film, and the difference between the maximum value and the minimum value of the film thickness was defined as a difference (Å) in the film thickness. The case where the difference in film thickness is within 200 angstroms is preferable.

According to the results of Examples 1 to 29, the photosensitive resin composition containing (L) a solvent having a low boiling point solvent content of 30 to 99 wt% and (H) 1 to 15 wt% of a high boiling point solvent has good halftone characteristics Thereby providing a cured film having a uniform film thickness.

According to the results of Comparative Examples 1 to 5, it was found that the photosensitive resin composition containing a solvent containing no (H) high boiling solvent did not provide a cured film having a uniform film thickness. According to the results of Comparative Examples 6 to 9, the photosensitive resin composition containing the (H) solvent containing no high-boiling solvent but containing (L) a low-boiling solvent content of less than 30% by weight does not provide a cured film having uniform film thickness . According to the results of Comparative Examples 7 and 9 to 11, it was found that the photosensitive resin composition containing a solvent in which the content of the (H) high boiling point solvent exceeds 15% by weight had inferior halftone characteristics.

[Examples 30 to 35]

Except that the respective contents (wt.%) Of the cardboard resin and the acrylic resin in the alkali-soluble resin, the type of solvent and the content (wt%) of each solvent were changed to the ratios shown in Table 5, To obtain a resin composition. Using the obtained photosensitive resin composition, the difference ΔH between the halftone characteristics and the film thickness difference was evaluated in the same manner as in the photosensitive resin composition of Example 9. The results of these evaluations are shown in Table 5. The results of Example 9 are shown in Table 5 for reference.

Comparing Examples 30, 33, and 34 with Examples 9, 31, and 35, when the alkali-soluble resin contains a cardo resin and an acrylic resin, the halftone characteristics It was found that this excellent photosensitive resin composition can be prepared.

Comparing Examples 9, 31 and 35 with Example 32, it can be seen that when the alkali-soluble resin contains a cardo resin and an acrylic resin, a black column spacer having a height equal to that of the case where the alkali- It is possible to prepare a photosensitive resin composition which is easy to form.

Claims (10)

(A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a light-
(L) a low boiling point solvent having a boiling point of less than 170 DEG C under atmospheric pressure and (H) a high boiling point solvent having a boiling point of 180 DEG C or higher at atmospheric pressure,
The content of the (L) low boiling solvent in the (S) solvent is 30 to 99% by weight,
The content of the (H) high boiling point solvent in the (S) solvent is 1 to 15% by weight. The method according to claim 1,
Wherein the boiling point of the high boiling point solvent (H) is 180 占 폚 or more and 300 占 폚 or less at atmospheric pressure. The method of claim 2,
Wherein the (H) high boiling solvent is 1,4-butanediol diacetate, diethylene glycol mono-n-butyl ether acetate, 1,6-hexanediol diacetate, epsilon -caprolactone, 1,3-butylene glycol diacetate , Diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol methyl-n-butyl ether,? -Butyrolactone, dipropylene glycol methyl-n-propyl ether and propylene glycol diacetate Wherein the photosensitive resin composition is at least one selected from the group consisting of a photosensitive resin composition and a photosensitive resin composition. The method according to any one of claims 1 to 3,
Wherein the boiling point of the (L) low-boiling solvent under atmospheric pressure is 100 占 폚 or more and less than 170 占 폚. The method of claim 4,
Wherein the (L) low boiling point solvent is at least one selected from the group consisting of propylene glycol monomethyl ether acetate, cyclohexanone, 3-methoxybutanol and cyclopentanone. The method according to any one of claims 1 to 5,
Wherein the alkali-soluble resin (A) comprises a resin having at least one of the structures represented by the following formulas (i) to (iii) and an acrylic resin.

A black column spacer formed from the photosensitive resin composition for a black column spacer according to any one of claims 1 to 6. A display device comprising the black column spacer according to claim 7. A method for manufacturing a black column spacer comprising the steps of applying a photosensitive resin composition for a black column spacer according to any one of claims 1 to 6 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. The method of claim 9,
A method of forming a black column spacer in which exposure is performed via a halftone mask in the exposure step.