JP2018156068A - Black photosensitive resin composition, column spacer produced using the same, color filter containing black matrix or black column spacer, and display device including the color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black photosensitive resin composition in which an adhesive force of a black matrix or black column spacer is improved.SOLUTION: There are provided a black photosensitive resin composition which contains (A) a colorant, (B) an alkali-soluble resin having a specific structure having a (meth)acrylate group in its side chain, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, where (C) the photopolymerizable compound contains a monomer having the number of functional groups of 4 to 7, and an acid value of (C) the photopolymerizable compound is 25-50 mgKOH/g; a column spacer produced using the same; a color filter containing a black matrix or black column spacer; and a display device including the color filter.SELECTED DRAWING: None

Description

The present invention relates to a black photosensitive resin composition, a column spacer manufactured using the same, a color filter including a black matrix, or a black column spacer, and a display device including the color filter.

The color filter is composed of three primary color pixels, a red pixel, a green pixel, and a blue pixel, and a black matrix that is formed at the boundary of each color pixel and does not substantially transmit visible light as black. The black matrix or black column spacer is a material that secures a space necessary for liquid crystal to move between the two glass plates constituting the LCD and maintains the elasticity of the LCD, and is formed of a black photosensitive resin composition. The black matrix or black column spacer must be columnar and can be provided at the desired location, allowing precise spacing and thickness adjustment. At this time, it is necessary to adjust the height of the black column spacer in consideration of the height of the element.

Conventionally, in order to form a black column spacer, a method of dispersing bead particles serving as a spacer over the entire surface of the substrate has been employed. However, this method has a drawback in that it is difficult to ensure a uniform cell gap and beads adhere to the pixel display portion, so that the contrast and image quality of the image are lowered. Therefore, in order to solve such a problem, various methods using a photosensitive resin composition capable of forming a step are proposed.

Patent Document 1 proposes a method of forming a black column spacer having a difference in height using a photosensitive resin composition, but has a drawback in that film adhesion is not sufficient.

Korean Published Patent No. 10-2012-0033893

The present invention has been made to solve the above-described problems of the prior art, and an object of the present invention is to provide a black photosensitive resin composition having improved adhesion of a black matrix or a black column spacer.

Another object of the present invention is to provide a column spacer manufactured using the black photosensitive resin composition, a color filter including a black matrix, or a black column spacer, and a display device including the color filter. .

In order to achieve the above object, (B) an alkali-soluble resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent, The alkali-soluble resin includes monomers of the following chemical formulas 1 and 2 at the same time, and the (C) photopolymerizable compound includes a monomer having a functional group number between 4 and 7, and the (C) photopolymerizable compound. An acid value of 25 to 50 mgKOH / g is provided, and a black photosensitive resin composition is provided.

In the monomer of Formula 1,
R ₁ is hydrogen or a methyl group;
R ₂ is a C ₁ -C ₂₀ alkylene group substituted by a hydroxy group;
R ₃ is a C _{1 to} C ₁₂ alkyl (meth) acrylate group.

In addition, the present invention provides a color filter including a column spacer, a black matrix, or a black column spacer manufactured using the black photosensitive resin composition.

Furthermore, the present invention provides a display device including the color filter.

The black photosensitive resin composition of the present invention provides an effect of improving the adhesion of a black matrix or black column spacer.

In addition, the column spacer manufactured using the black photosensitive resin composition, the color filter including the black matrix, or the black column spacer, and the display device including the color filter have excellent characteristics in terms of drivability and durability. I will provide a.

The present invention comprises (A) a colorant; (B) an alkali-soluble resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent. The monomer of the following Chemical Formula 1 and Chemical Formula 2 are included at the same time, the (C) photopolymerizable compound includes a monomer having a functional group number between 4 and 7, and the acid value of the (C) photopolymerizable compound is: Provided is a black photosensitive resin composition, which is 25 to 50 mg KOH / g.

In the monomer of Formula 1,
R ₁ is hydrogen or a methyl group;
R ₂ is a C ₁ -C ₂₀ alkylene group substituted by a hydroxy group;
R ₃ is a C _{1 to} C ₁₂ alkyl (meth) acrylate group.

Preferably, in the monomer of Formula 1,
R ₁ is a methyl group;
R ₂ is a C ₁ -C ₂₀ alkylene group substituted by a hydroxy group, more preferably a linear or branched C ₁ -C ₁₀ alkylene group substituted by a hydroxy group;
R ₃ may be acrylate or methyl acrylate.

In the black photosensitive resin composition of the present invention, (B) the alkali-soluble resin simultaneously contains monomers of the following chemical formula 1 and chemical formula 2, and the (C) photopolymerizable compound has 4 to 7 functional groups. And (C) the photopolymerizable compound has an acid value of 25 to 50 mg KOH / g, thereby improving the adhesion of a black matrix or a black column spacer produced using the monomer. It is greatly improved.

Hereinafter, each component which comprises the black photosensitive resin composition of this invention is demonstrated. However, the present invention is not limited by these components.

(A) Colorant The colorant is used to realize black color, and imparts light shielding properties to all of the spacer, the black matrix, and the black column spacer. The black column spacer means that the column spacer and the black matrix are integrally formed. That is, the black matrix can play a role of preventing light leakage, and the spacer can play a role of preventing malfunction of the device due to light caused from the outside.

As the colorant, any colorants known in this field such as organic pigments, dyes, and black pigments can be used as long as they have a light-shielding property in visible light, and black pigments may be used. preferable.

As the black pigment, known pigments can be used without any particular limitation. Specifically, aniline black, perylene black, titanium black, carbon black, and the like can be used. These can be used alone or in combination of two or more. Examples of the carbon black include channel black, furnace black, thermal black, and lamp black.

If necessary, carbon black whose surface is coated with a resin can be used for electrical insulation. In addition, carbon black coated with resin is less conductive than carbon black not coated with resin, so it is excellent when forming black matrix, spacer, or black column spacer (black matrix integrated spacer). Electrical insulation can be imparted.

The colorant may optionally further include a color correction agent as necessary. As the color corrector, condensed polycyclic pigments such as anthraquinone pigments or perylene pigments, organic pigments such as phthalocyanine pigments or azo pigments can be used, anthraquinone pigments or phthalocyanine pigments are preferable, and phthalocyanine pigments are more preferable. . Examples of phthalocyanine pigments include C.I. Pigment Blue 15: 6, C.I. Pigment Blue 15: 4, C.I. I Pigment Blue 16 and examples of anthraquinone pigments include C.I. I pigment blue 60 is mentioned. Examples of the phthalocyanine pigment include C.I. I Pigment Blue 15: 6 may be preferred.

The colorant (A) is one or more organic black pigments selected from the group consisting of lactam black, aniline black, and perylene black; one or more inorganics selected from the group consisting of titanium black and carbon black Black pigments; and blue pigments.

Among organic black pigments, use of lactam black (eg, Irgaphor (R) Black S0100CF manufactured by Bassf) may be preferable in terms of optical density, dielectric constant, transmittance, and the like.

Among the inorganic black pigments, it may be preferable to use carbon black in terms of pattern characteristics and chemical resistance.

Among the blue pigments, C.I. It may be preferable to use I Pigment Blue 15: 6 in order to prevent light leakage.

The colorant is contained in an amount of 1 to 50% by weight, preferably 5 to 20% by weight, based on the total weight of the black photosensitive resin composition. When the colorant is contained in an amount of 1 to 50% by weight, the optical density is excellent, and in the case of 5 to 20% by weight, the optical density can be further improved.

In this invention, solid content in a black photosensitive resin composition means the sum total of the component which removed the solvent.

The colorant is preferably a pigment dispersion in which the pigment particle size is uniformly dispersed. Examples of the method for uniformly dispersing the pigment particle size include a method of dispersing by adding a pigment dispersant (a1). The pigment is uniformly dispersed in the solution by the above method. A pigment dispersion can be obtained.

(A1) Pigment dispersant The pigment dispersant is added to disaggregate and maintain the stability of the pigment. Specific examples of the pigment dispersant include cationic, anionic, nonionic, and amphoteric. These include surfactants such as polyesters, polyesters, and polyamines, and these can be used alone or in combination of two or more.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, or quaternary ammonium salts.

Specific examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, and the like. And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan Examples include fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Other examples include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines.

The pigment dispersant preferably contains an acrylate dispersant (hereinafter referred to as an acrylate dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). It is preferable to use the acrylate-based dispersant produced by the living control method. Examples of commercially available products include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150. The acrylate dispersants can be used alone or in admixture of two or more.

In addition to the acrylate-based dispersant, other resin-type pigment dispersants may be used as the pigment dispersant. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, particularly polyurethanes, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, and polycarboxylic acid (partial). ) Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl groups-containing polycarboxylic acids and their modified products, or free ) Oily dispersants such as amides or their salts formed by the reaction of polyesters with carboxyl groups and poly (lower alkyleneimines); (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- ( (Meth) acrylate ester copolymer, styrene-ma Ynoic acid copolymers, polyvinyl alcohol or water-soluble resin or a water-soluble polymeric compounds such as polyvinyl pyrrolidone, polyesters, modified polyacrylate; ethylene oxide / propylene oxide addition product of; and and phosphate esters.

As a commercial product of the pigment dispersant of the other resin type, as the cationic resin dispersant, for example, trade names of BYK (Big) Chemie: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162 , DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF Corporation trade names: EFKA-44, EFKA-46, EFKA-47, EFKA -48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406 EFKA-4510, EFKA-4800; trade names of Lubilzol: SOLPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; trade names of Kawaken Fine Chemicals: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Ajinomoto brand names: AJISPUR PB-821, Ajisper PB-822, Azisper PB-823; Kyoeisha Chemical brand names: FLORENE DOPA-17HF, FLOREN DOPA-15BHF, FLOREN DOPA -33, florene DOPA-44 and the like.

In addition to the acrylate-based dispersant, other resin-type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylate-based dispersant.

The pigment dispersant is included in an amount of more than 0 and 1 part by weight or less, preferably 0.01 to 0.5 parts by weight with respect to 1 part by weight of the colorant. When the pigment dispersant is contained in an amount of more than 0 and not more than 1 part by weight, it is preferable because a uniformly dispersed pigment can be obtained.

(B) Alkali-soluble resin The alkali-soluble resin has reactivity and alkali solubility due to the action of light and heat, acts as a solid dispersion medium including a colorant, and functions as a binder resin. As the alkali-soluble resin, a binder that can be dissolved in an alkaline developer used in the development stage of film production can be used.

The alkali-soluble resin used in the present invention is characterized by containing monomers of the following chemical formulas 1 and 2 at the same time. That is, it may be a copolymer containing the monomer.

In the monomer of Formula 1,
R ₁ is hydrogen or a methyl group;
R ₂ is a C ₁ -C ₂₀ alkylene group substituted by a hydroxy group;
R ₃ is a C _{1 to} C ₁₂ alkyl (meth) acrylate group.

In the present invention, the “alkyl (meth) acrylate” means “alkyl acrylate” or “alkyl methacrylate”.

Preferably, the alkali-soluble resin is not only the monomer of Chemical Formula 1 and Chemical Formula 2, but also a monomer containing a carboxyl group, and other monomers copolymerizable with the monomer containing a carboxyl group. The copolymer further contains a monomer.

R ₁ is a methyl group; R ₂ is a C ₁ -C ₁₀ alkylene group substituted by a hydroxy group; R ₃ may be preferred in terms of adhesion in the case of acrylate or methyl acrylate .

In the (B) alkali-soluble resin, the content of the monomer of Formula 1 may be 20 to 60% by weight, preferably 30 to 50% by weight based on the total content of the (B) alkali-soluble resin. The content of the monomer represented by Chemical Formula 2 may be 30 to 60% by weight, preferably 35 to 50% by weight, based on the total content of the (B) alkali-soluble resin. There may be. (B) In the alkali-soluble resin, the content of the monomer of Formula 1 is 20 to 60% by weight with respect to the total content of the (B) alkali-soluble resin, and the content of the monomer of Formula 2 is (B) In the case of 30 to 60% by weight based on the total content of the alkali-soluble resin, it may be advantageous in terms of increasing the adhesion of the black matrix or black column spacer produced using the same, (B) In the alkali-soluble resin, the content of the monomer of Chemical Formula 1 is 30 to 50% by weight with respect to the total content of the (B) alkali-soluble resin, and the content of the monomer of Chemical Formula 2 is (B When the content is 35 to 50% by weight based on the total content of the alkali-soluble resin, it may be further advantageous in terms of increasing the adhesion of the black matrix or black column spacer produced using the resin.

The (B) alkali-soluble resin can additionally be copolymerized with a carboxyl group-containing monomer that can be copolymerized with the monomer represented by Chemical Formula 1 or Chemical Formula 2, or with a carboxyl group-containing monomer. You may further contain the compound containing another monomer 5 to 50weight% with respect to the total weight of (B) alkali-soluble resin. That is, in addition to the monomer represented by Chemical Formula 1 or Chemical Formula 2, another monomer (compound) is additionally added and copolymerized to produce (B) the alkali-soluble resin of the present invention. be able to.

The weight ratio of the monomer of Formula 1 to the monomer of Formula 2 may be 20 to 60:30 to 60.

Examples of the carboxyl group-containing monomer include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated carboxylic acids having one or more carboxyl groups in the molecule, such as unsaturated tricarboxylic acids.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like.

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

The unsaturated polyvalent carboxylic acid may be an acid anhydride, and specific examples include maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate. ), Mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, and the like. The unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. It is done.

The said carboxyl group-containing monomer can be used individually or in mixture of 2 or more types, respectively.

Examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o -Methoxy styrene, m-methoxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p -Aromatic vinyl compounds such as vinylbenzyl glycidyl ether and indene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl Pill methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2 -Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxy Butyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acetate Relate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate , Methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate , Isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol mono Unsaturated carboxylic acid esters such as methacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopro Unsaturated carboxylic acid aminoalkyl esters such as dimethyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; vinyl acetate, vinyl propionate and butyric acid Carboxylic acid vinyl esters such as vinyl and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide Compound: acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl methacrylate Unsaturated amides such as amide; unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; and polystyrene, polymethyl acrylate, Polymers of polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane, giant monomers having a monoacryloyl group or a monomethacryloyl group at the end of the molecular chain, glycidyl acrylate, glycidyl methacrylate Glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate, β-ethyl glycidyl acrylate , Glycidyl acrylates such as methacrylic acid-β-ethyl glycidyl, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, methacrylic acid-6 , 7-epoxyheptyl, epoxyalkyl acrylates such as α-ethylacrylic acid-6,7-epoxyheptyl; vinylbenzyl such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether Examples thereof include glycidyl ethers. These monomers can be used alone or in admixture of two or more.

Preferably, the alkali-soluble resin having an acid value of 20 to 200 (KOH mg / g) is selected and used. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and is involved in solubility. When the acid value of the resin falls within the above range, the solubility in the developer is improved, the non-exposed portion is easily dissolved, and the sensitivity is increased. As a result, the pattern of the exposed portion remains at the time of development and the remaining film ratio There is an advantage that (film retaining ratio) is improved.

In addition, the alkali-soluble resin can take into consideration limitations on molecular weight and molecular weight distribution (MW / MN) in order to improve surface hardness. Preferably, the weight average molecular weight is 3,000 to 200,000, more preferably 5,000 to 100,000, still more preferably 5,000 to 30,000, and the molecular weight distribution is 1.5 to It is directly polymerized so as to have a range of 6.0, preferably 1.8 to 4.0, or purchased and used. The alkali-soluble resin having a molecular weight and a molecular weight distribution in the above range has high hardness, high residual film ratio, and excellent solubility in non-exposed portions in the developer, thereby improving resolution.

The alkali-soluble resin can be used in an amount of 5 to 80% by weight, preferably 7 to 50% by weight, based on the total weight of the black photosensitive resin composition. This content is a range selected in consideration of the solubility in the developer and pattern formation, and when used within the above range, the solubility in the developer is sufficient and pattern formation is easy. In addition, a reduction in the film thickness of the pixel portion of the exposed portion is prevented during development, and the omission of the non-pixel portion is improved.

(C) Photopolymerizable compound The photopolymerizable compound is a component for enhancing the strength of the pattern, and is a monomer having a functional group number between 4 and 7, and the acid value of the (C) photopolymerizable compound. Is 25-50 mg KOH / g. When the acid value of the photopolymerizable compound is 25 mgKOH / g to 50 mgKOH / g, the adhesion to the substrate is further increased.

Specific examples of monomers having 4 to 7 functional groups include pentaerythritol tetra (meth) acrylic acid, dimethylolpropanetetra (methyl) acrylic acid, dipentaerythritol penta (meth) acrylic acid, dipentaerythritol hexa ( (Meth) acrylic acid, butanedioic acid, dipentaerythritol acrylate ester, pentaerythritol tetra (meth) acrylate ester, dimethylolpropane tetra (methyl) acrylate ester, dipentaerythritol penta (meth) acrylate ester, dipenta Examples include monomers such as erythritol hexa (meth) acrylate. These can be used individually or in mixture of 2 or more types.

The photopolymerizable compound can be used in an amount of 1 to 30% by weight, preferably 2 to 15% by weight, based on the total weight of the black photosensitive resin composition. The photopolymerizable compound can improve the strength and flatness of the pixel portion in the range of 1 to 30% by weight, and can further improve the strength and flatness of the pixel portion in the range of 2 to 15% by weight. .

(D) Photopolymerization initiator The photopolymerization initiator is a compound for initiating polymerization of the photopolymerizable compound, and is not particularly limited in the present invention. However, acetophenone, benzophenone, triazine, thioxanthone, oxime A system, a benzoin system, an anthraquinone system, a biimidazole system, etc. can be used, and these can be used individually or in mixture of 2 or more types.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl]- 2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) butan-1-one, oligomers of 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl] propan-1-one, and the like. Among these, in particular, 2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one is preferably used It can be.

Examples of the benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino). ) Benzophenone.

Examples of the triazine compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trimethyl) -s-triazine, and 2- (3 ′, 4′-dimethoxystyryl). -4,6-bis (卜 trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (卜 -trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (卜 lichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (卜 lichloromethyl) -s-triazine, 2-biphenyl-4,6-bis (卜 lichloromethyl) -s- Triazine, bis (卜 lichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (卜 lichloromethyl) -s-triazine, 2- (4-me Xylnaphtho-1-yl) -4,6-bis (卜 lichloromethyl) -s-triazine, 2,4- 卜 trichloromethyl (piperonyl) -6-triazine, 2,4- 卜 trichloromethyl (4′-methoxystyryl) -6 Examples include triazine.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

Examples of the oxime compounds include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and commercially available products include Irgacure OXE01 and Irgacure OXE02 manufactured by Basf.

As the benzoin compound, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, or the like can be used.

Examples of the anthraquinone compound include 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone.

Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxyphenyl) biimidazole, imidazole compounds in which the phenyl groups at the 4,4 ′, 5,5 ′ positions are substituted by carboalkoxy groups, etc. Is mentioned.

The photopolymerization initiator has a high sensitivity in the range of 0.01 to 10% by weight, and the strength of the pixel portion formed using the black photosensitive resin composition and the straightness of the pattern are improved. It can be even better in the range of 01 to 5 wt%.

The photopolymerization initiator may be used in combination with a photopolymerization initiation auxiliary agent. When a photopolymerization initiator auxiliary agent is used in combination with the photopolymerization initiator, the sensitivity of the black photosensitive resin composition containing these is further increased, and when this is used to form a cell gap maintaining support spacer, the productivity is improved. Since it improves, it is preferable.

The photopolymerization initiation auxiliary agent can be used to increase the polymerization efficiency, and amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and the like can be used.

Examples of the amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. 2-dimethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4 Examples include '-bis (ethylmethylamino) benzophenone, and 4,4'-bis (diethylamino) benzophenone is particularly preferable.

Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

The photopolymerization initiation auxiliary agent can be directly manufactured or purchased and used. For example, the product name “EAB-F” [manufacturer: Hodogaya Chemical Co., Ltd.] series is used. can do.

The photopolymerization initiation assistant is usually used in an amount of 10 mol or less, preferably 0.01 to 5 mol, per mol of the photopolymerization initiator. When the photopolymerization initiation auxiliary is used within the above range, it is possible to increase the polymerization efficiency and expect an improvement in productivity.

(E) Solvent Any solvent can be used as long as it can dissolve or disperse the above-mentioned composition, and is not particularly limited in the present invention. Preferably, an organic solvent having a boiling point of 100 to 200 ° C. can be used in terms of coating properties and drying properties.

Typically, usable solvents include alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower and higher alcohols, cyclic esters and the like. More specifically, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol di Diethylene glycol dialkyl ethers such as butyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxy Alkylene glycol alkyl ether acetates such as butyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; ethanol, propanol and butanol , Alcohols such as hexanol, cyclohexanol, ethylene glycol and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone.

Among the solvents, alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate can be used, more preferably propylene glycol monomethyl ether. Acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like can be used. These solvents can be used alone or in combination of two or more.

The solvent is included in the remaining amount so that the black photosensitive resin composition satisfies 100% by weight. Such a content is a range selected in consideration of the dispersion stability of the composition and process ease (eg, applicability) in the production process. In other words, the black photosensitive resin composition according to the present invention can produce a black matrix, a spacer or a black column spacer (black matrix integrated spacer) by wet coating. At this time, as a wet coating method, a roll coater is used. A coating apparatus such as a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), and an ink jet can be used.

(F) Additive The black photosensitive resin composition may further contain additives known in this field for various purposes. Examples of such additives include dispersants, dispersion aids, surfactants, fillers, other polymer compounds, ultraviolet absorbers, and aggregation inhibitors. These additives can be used alone or in combination of two or more, and are preferably used in an amount of 5% by weight or less based on the total weight of the black photosensitive resin composition in consideration of light efficiency and the like.

Commercially available dispersants can be used as the dispersant, such as “DISPER BYK-163”, “DISPER BYK-170” manufactured by BYK, and “DISPER BYK-170”. “DISPER BYK-2000”; and Ciba Specialties Chemicals Corp. “Efka-1101 (EFKA-1110)” and “Efka-4310 (EFKA-4310)” included.

As the dispersion aid, commercially available dispersion aids can be used, and preferable examples include Lubrisol Solsperse 5000, Solsperse 12000, Solsperse 22000, and the like. This material is a copper phthalocyanine pigment derivative, and by giving affinity to carbon black, it helps electrical and chemical adsorption between the carbon black surface and the dispersant, compared to when using the dispersant alone. An effect of improving dispersibility and dispersion stability can be obtained.

A commercially available surfactant can be used as the surfactant, and a fluorine-based surfactant can be preferably used. Examples of the fluorosurfactant include BM-1000, BM-1100 (BM Chemie), Florard FC-135 / FC-170C / FC-430 (Sumitomo 3M), SH-28PA / -190 / SZ. -6032 (Toray Silicone Co., Ltd.) can be used.

As the filler, glass, silica, alumina and the like can be used, and other polymer compounds include curable resins such as epoxy resin and maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, Thermoplastic resins such as polyfluoroalkyl acrylate, polyester, and polyurethane can be used.

As the ultraviolet absorber, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, or the like can be used. As the aggregation inhibitor, polyacrylic acid can be used. Sodium or the like can be used.

The production of the black photosensitive composition of the present invention is not particularly limited, and depends on a known method for producing a black photosensitive composition.

As an example, after adding a colorant to a solvent, the remaining composition and other additives can be added and obtained by stirring. At this time, the colorant is added in the form of a mill base in which a pigment or the like is previously dissolved or dispersed in a solvent or an alkali-soluble resin. In the case of a solution form, the additive may be added in advance to the solvent together with the colorant.

The black photosensitive resin composition thus produced is preferably used for the production of a display device, preferably a black matrix of a liquid crystal display device, a spacer for maintaining a cell gap, or a black column spacer (black matrix integrated spacer). Can be used.

In particular, the black photosensitive resin composition of the present invention can be preferably used for the production of a black column spacer (black matrix integrated spacer), and the black column spacer (black matrix integrated spacer) comprises a black matrix and a spacer. Instead of forming each, it is formed in a structure that can play the roles of the black matrix and spacers in one pattern.

The present invention also relates to a color filter including a column spacer, a black matrix, or a black column spacer manufactured using the black photosensitive resin composition.

Furthermore, the present invention relates to a display device including the color filter.

A typical patterning process for forming a black matrix, a spacer, or a black column spacer (black matrix integrated spacer) by a photolithography method includes the following steps.
a) applying a black photosensitive resin composition to the substrate;
b) a pre-bake step of drying the solvent;
c) applying a photomask on the resulting coating and irradiating with active light to cure the exposed area;
d) performing a development step of dissolving the unexposed portion using an aqueous alkali solution;
e) Drying and post-baking execution steps.

As the substrate, a glass substrate or a polymer plate is used. As the glass substrate, in particular, soda-lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, or quartz can be preferably used. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

At this time, the coating is performed by a wet coating method using a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), or an ink jet so as to obtain a desired thickness.

Pre-baking is performed by heating with an oven, a hot plate, or the like. At this time, the heating temperature and heating time in prebaking are suitably selected according to the solvent to be used, for example, it is performed at a temperature of 80 to 150 ° C. for 1 to 30 minutes.

The exposure performed after the pre-baking is performed by an exposure device, and only the portion corresponding to the pattern is exposed by exposing through a photomask. At this time, the irradiated light can be, for example, visible light, ultraviolet light, X-rays, and electron beams.

This is performed for the purpose of removing the photosensitive resin composition in the unexposed portion of the alkali-development non-exposed portion after exposure, and a desired pattern is formed by this development. As a developer suitable for the alkali development, for example, an alkali metal or alkaline earth metal carbonate aqueous solution or the like can be used. In particular, using an alkaline aqueous solution containing 1 to 3% by weight of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate, a developing machine or an ultrasonic cleaning machine at a temperature of 10 to 50 ° C., preferably 20 to 40 ° C. Etc.

Post-baking is performed to increase the adhesion between the patterned film and the substrate, and is performed by heat treatment at 80 to 220 ° C. for 10 to 120 minutes. Post-baking is performed using an oven, a hot plate, or the like, as in pre-baking.

At this time, the film thickness of the black matrix is preferably 0.2 μm to 10.0 μm, more preferably 0.5 μm to 7.0 μm, and particularly preferably 1.0 μm to 5.0 μm.

The film thickness of the column spacer and the black column spacer (black matrix integrated spacer) is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and particularly preferably 0.1 μm to 4 μm.

The black matrix, spacer or black column spacer (black matrix integrated spacer) produced with the black photosensitive resin composition of the present invention has the effect of improving the adhesion of the black matrix or black column spacer to the substrate, The display device can have excellent characteristics in terms of drivability and durability.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for explaining the present invention more specifically, and the scope of the present invention is not limited by the following examples. The following embodiments can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Production Example 1: Alkali-soluble resin (B1) containing monomers represented by Chemical Formulas 1 and 2
To a four-necked flask equipped with a dropping funnel, thermometer, condenser, and stirrer, 3,4-epoxytricyclodecan-8-yl (meth) acrylate and 3,4-epoxytricyclodecan-9-yl (meta ) 30 parts by weight of a mixture obtained by mixing acrylate with 50:50, 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyltoluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate Then, 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added dropwise over 1 hour, and the polymerization reaction was allowed to proceed for 0.5 hour. Next, a mixed solution of 15 parts by weight of methacrylic acid, 10 parts by weight of methyl methacrylate, 70 parts by weight of propylene glycol methyl ether, and 3 parts by weight of 2,2′-azobisisobutyronitrile is gradually added dropwise over 1 hour. Then, after carrying out the polymerization for 8 hours, it was allowed to cool at room temperature. After replacing the inside of the four-necked flask with nitrogen, 65 parts by weight of glycidyl methacrylate, 3 parts by weight of tetra-n-butylammonium bromide, and 2 parts by weight of methoquinone were added to the flask, and the reaction was carried out at 80 ° C. for 12 hours. Thus, an alkali-soluble resin B1 was obtained. The weight average molecular weight of B1 measured by GPC was 23,000.

Production Example 2: Alkali-soluble resin (B2) containing monomers represented by Chemical Formulas 1 and 2
To a four-necked flask equipped with a dropping funnel, thermometer, condenser, and stirrer, 3,4-epoxytricyclodecan-8-yl (meth) acrylate and 3,4-epoxytricyclodecan-9-yl (meta ) 30 parts by weight of a mixture obtained by mixing acrylate with 50:50, 30 parts by weight of methyl methacrylate, 55 parts by weight of acrylic acid, 65 parts by weight of vinyltoluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate Then, 50 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added dropwise over 1 hour, and the polymerization reaction was allowed to proceed for 0.5 hour. Next, a mixed solution of 25 parts by weight of methacrylic acid, 15 parts by weight of methyl methacrylate, 50 parts by weight of propylene glycol methyl ether, and 3 parts by weight of 2,2′-azobisisobutyronitrile is gradually added dropwise over 1 hour. Then, after carrying out the polymerization for 8 hours, it was allowed to cool at room temperature. After replacing the inside of the four-necked flask with nitrogen, 70 parts by weight of glycidyl methacrylate, 3 parts by weight of tetra-n-butylammonium bromide, and 2 parts by weight of methoquinone were added to the flask, and the reaction was carried out at 80 ° C. for 12 hours. Thus, an alkali-soluble resin B2 was obtained. The weight average molecular weight of B2 measured by GPC was 22,400.

Production Example 3: Alkali-soluble resin (B3) containing monomers represented by Chemical Formulas 1 and 2
To a four-necked flask equipped with a dropping funnel, thermometer, condenser, and stirrer, 3,4-epoxytricyclodecan-8-yl (meth) acrylate and 3,4-epoxytricyclodecan-9-yl (meta ) 15 parts by weight of a mixture prepared by mixing acrylate with a molar ratio of 50:50, 15 parts by weight of methyl methacrylate, 70 parts by weight of acrylic acid, 60 parts by weight of vinyltoluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate 60 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added dropwise over 1 hour, and the polymerization reaction was allowed to proceed for 0.5 hour. Next, a mixed solution of 30 parts by weight of methacrylic acid, 20 parts by weight of methyl methacrylate, 40 parts by weight of propylene glycol methyl ether, and 3 parts by weight of 2,2′-azobisisobutyronitrile is gradually added dropwise over 1 hour. Then, after carrying out the polymerization for 8 hours, it was allowed to cool at room temperature. After replacing the inside of the four-necked flask with nitrogen, 80 parts by weight of glycidyl methacrylate, 3 parts by weight of tetra-n-butylammonium bromide, and 2 parts by weight of methoquinone were added to the flask, and the reaction was carried out at 80 ° C. for 12 hours. Thus, an alkali-soluble resin B3 was obtained. The weight average molecular weight of B3 measured by GPC was 24,200.

Production Example 4: Alkali-soluble resin (B4) containing monomers represented by Chemical Formulas 1 and 2
To a four-necked flask equipped with a dropping funnel, thermometer, condenser, and stirrer, 3,4-epoxytricyclodecan-8-yl (meth) acrylate and 3,4-epoxytricyclodecan-9-yl (meta ) 30 parts by weight of a mixture prepared by mixing acrylate with a molar ratio of 50:50, 65 parts by weight of methyl methacrylate, 35 parts by weight of acrylic acid, 70 parts by weight of vinyltoluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate Then, 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added dropwise over 1 hour, and the polymerization reaction was allowed to proceed for 0.5 hour. Next, a mixed solution of 15 parts by weight of methacrylic acid, 10 parts by weight of methyl methacrylate, 60 parts by weight of propylene glycol methyl ether, and 3 parts by weight of 2,2′-azobisisobutyronitrile is gradually added dropwise over 1 hour. Then, after carrying out the polymerization for 8 hours, it was allowed to cool at room temperature. After replacing the inside of the four-necked flask with nitrogen, 65 parts by weight of glycidyl methacrylate, 3 parts by weight of tetra-n-butylammonium bromide, and 2 parts by weight of methoquinone were added to the flask, and the reaction was carried out at 80 ° C. for 12 hours. Thus, an alkali-soluble resin B4 was obtained. The weight average molecular weight of B4 measured by GPC was 22,900.

Production Example 5: Alkali-soluble resin (B5) containing monomers represented by Chemical Formulas 1 and 2
To a four-necked flask equipped with a dropping funnel, thermometer, condenser, and stirrer, 3,4-epoxytricyclodecan-8-yl (meth) acrylate and 3,4-epoxytricyclodecan-9-yl (meta ) 15 parts by weight of a mixture of acrylate and 50:50, 10 parts by weight of methyl methacrylate, 60 parts by weight of acrylic acid, 65 parts by weight of vinyltoluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate Then, 55 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added dropwise over 1 hour, and the polymerization reaction was allowed to proceed for 0.5 hour. Next, a mixed solution of 25 parts by weight of methacrylic acid, 15 parts by weight of methyl methacrylate, 70 parts by weight of propylene glycol methyl ether, and 3 parts by weight of 2,2′-azobisisobutyronitrile is gradually added dropwise over 1 hour. Then, after carrying out the polymerization for 8 hours, it was allowed to cool at room temperature. After replacing the inside of the four-necked flask with nitrogen, 75 parts by weight of glycidyl methacrylate, 3 parts by weight of tetra-n-butylammonium bromide, and 2 parts by weight of methoquinone were added to the flask, and the reaction was carried out at 80 ° C. for 12 hours. Thus, an alkali-soluble resin B5 was obtained. The weight average molecular weight of B5 measured by GPC was 24,900.

Examples 1-5 and Comparative Examples 1-3
After adding a solvent to the mixer, a pigment, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other additives are added and mixed uniformly by stirring to produce a black photosensitive resin composition. did. At this time, the composition followed the composition shown in Table 2 below.

The obtained photosensitive resin composition was applied onto a glass substrate by a spin coating method, then placed on a heating plate and maintained at a temperature of 100 ° C. for 2 minutes to remove the solvent.

Next, the thin film was irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated with light using an ultrahigh pressure mercury lamp (trade name USH-250D) manufactured by USHIO ELECTRIC CO., LTD. At an exposure amount (365 nm) of 40 mJ / cm ^{2 in} an air atmosphere. An optical filter was not used.

The thin film irradiated with ultraviolet rays was developed in a KOH aqueous solution developing solution having a pH of 12.5 for 60 seconds using a spray developing machine, and then heated in a 230 ° C. heating oven for 20 minutes to produce a pattern. The thickness of the manufactured film was 3.2 μm.

note)
1) C.I. Pigment Blue 15: 4, product of DIC 2) Irgaphor (R) Black S0100CF (Organic Black), product of BASF 3) CB (MA-8), product of Mitsubishi Corp. 4) 5.5 functional, acid value 26.9 mgKOH / G, Shin-Nakamura Chemical 5) 5.5 functional, acid value 0 mgKOH / g, Shin-Nakamura Chemical 6) Trifunctional, acid 0 mg KOH / g, Shin-Nakamura 7) 8-functional, acid 0 mg KOH / g, Osaka Organic Chemical Product 8) 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone-1- (O-acetyloxime), Ciba product 9) BYK product 10) Lubrisol products 11) Propylene glycol monomethyl ether acetate

Experimental Example 1: Measurement of adhesion force 5 cm × 5 cm glass substrate (Corning) was washed with a neutral detergent and water and then dried. On the glass substrate, each of the black photosensitive resin compositions produced in Examples 1 to 5 and Comparative Examples 1 to 3 was spin-coated so that the final film thickness was 3.0 μm, and 80 to 120 Pre-baked at 0 ° C. and dried for 1-2 minutes to remove the solvent. Thereafter, the entire surface is exposed at an exposure amount of 40 to 150 mJ / cm ² , and then foreign matter on the surface is removed using an alkaline aqueous solution, followed by post-baking at 200 to 250 ° C. for 10 to 30 minutes to produce a colored substrate. did.

The colored substrate and the glass substrate (Corning) are each cut to a size of 25 mm × 50 mm, and one drop of a thermosetting sealant (sealant) is applied to the center of the cut colored substrate (25 mm × 50 mm). After dripping, the glass substrate (25 mm × 50 mm) cut in such a manner that the dropped sealant came to the center and the diameter became 0.5 mm was bonded to the colored substrate. Thereafter, the substrate was left for 2 minutes, exposed at 7000 mJ / cm ² , and then cured at 120 ° C. for 1 hour to produce an evaluation substrate.

With the test substrate being fixed on the evaluation substrate with UTM (Universal testing machine, Instron) equipment, the force when the glass substrate was peeled off by pressing 3 mm / min with Probe was measured. At this time, the adhesion (N / mm ² ) is a value obtained by dividing the measured value (N) when the colored substrate is separated from the glass substrate by the sealant adhesion area (mm ² ).

[Judgment criteria]
○: Glass crack or contact strength 2N / mm ² or more ×: contact strength 2N / mm ^{2 or} less

Referring to Table 3 above, the adhesion of the black photosensitive resin compositions of Examples 1 to 5 was excellent in adhesion with a standard value of 2.0 N / mm ² or more, whereas The compositions of Comparative Examples 1 to 3 were less than the reference value, and it was confirmed that the adhesion was insufficient.

Claims (11)

(A) a colorant;
(B) an alkali-soluble resin;
(C) a photopolymerizable compound;
(D) a photopolymerization initiator; and (E) a solvent,
Said (B) alkali-soluble resin contains the monomer of the following Chemical formula 1 and Chemical formula 2 simultaneously,
The (C) photopolymerizable compound includes a monomer having a functional group number between 4 and 7,
The black photosensitive resin composition, wherein the acid value of the photopolymerizable compound (C) is 25 to 50 mgKOH / g.

(In the formula, in the monomer of Formula 1,
R ₁ is hydrogen or a methyl group;
R ₂ is a C ₁ -C ₂₀ alkylene group substituted by a hydroxy group;
R ₃ is a C _{1 to} C ₁₂ alkyl (meth) acrylate group. ) In the monomer of Formula 1,
R ₁ is a methyl group;
R ₂ is a C ₁ -C ₁₀ alkylene group substituted by a hydroxy group;
The black photosensitive resin composition according to claim 1, wherein R ₃ is acrylate or methyl acrylate. The black photosensitive resin composition according to claim 1, wherein the monomer of Formula 1 is a compound of Formula 3.

2. The black photosensitive resin composition according to claim 1, wherein a weight ratio of the monomer of Formula 1 to the monomer of Formula 2 is 20 to 60:30 to 60. 3. 2. The black photosensitive resin composition according to claim 1, wherein the (B) alkali-soluble resin has a molecular weight of 3,000 to 200,000. 2. The black photosensitive resin according to claim 1, wherein the colorant (A) is at least one selected from the group consisting of aniline black, perylene black, titanium black, and carbon black. Composition. The colorant (A) is one or more organic black pigments selected from the group consisting of lactam black, aniline black, and perylene black; one or more inorganics selected from the group consisting of titanium black and carbon black The black photosensitive resin composition according to claim 1, comprising a black pigment; and a blue pigment. With respect to the total weight of the composition,
(A) 1 to 50% by weight of a colorant;
(B) Alkali-soluble resin 5 to 80% by weight;
(C) 1-30% by weight of a photopolymerizable compound;
2. The black photosensitive resin composition according to claim 1, comprising (D) a photopolymerization initiator in an amount of 0.01 to 10% by weight; and (E) a remaining amount of a solvent. The black photosensitive resin composition includes at least one (F) selected from the group consisting of a dispersant, a dispersion aid, a surfactant, a filler, another polymer compound, an ultraviolet absorber, and an aggregation inhibitor. 2) The black photosensitive resin composition according to claim 1, further comprising an additive. The color filter containing the column spacer manufactured using the black photosensitive resin composition of Claim 1, a black matrix, or a black column spacer. A display device comprising the color filter according to claim 10.