KR102112320B1 - Black photo sensitive resin composition with stair difference and color filter manufacturing method using the same - Google Patents

Abstract

The present invention is a colorant (A) containing a black pigment, a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), at least one compound (E) and a solvent selected from melamine-based and ureaaldehyde-based solvents ( F), a method for manufacturing a liquid crystal display device comprising a black photosensitive resin composition and a black matrix and a black column spacer formed thereon, which are capable of forming a sufficient level difference through a difference in exposure amount using a halftone mask, wherein the black The photosensitive resin composition has an advantage of high adhesion to a substrate.

Description

A black photosensitive resin composition capable of forming a step and a manufacturing method of a color filter using the same {BLACK PHOTO SENSITIVE RESIN COMPOSITION WITH STAIR DIFFERENCE AND COLOR FILTER MANUFACTURING METHOD USING THE SAME}

The present invention includes a coloring material containing a black pigment (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a melamine-based or ureaaldehyde-based compound (E) and a solvent (F) It comprises a black photosensitive resin composition capable of forming a level difference, characterized in that it relates to a color filter comprising a black matrix or a black column spacer formed therefrom, and a liquid crystal display device having the same and a method of manufacturing the same.

The color filter is formed of three primary color color pixels of 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 the space required for the liquid crystal to move between the two glass plates constituting the LCD and maintains the LCD elasticity, and is formed from a black photosensitive resin composition. The black matrix or black column spacer can be installed wherever desired in a column shape, 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 device.

Conventionally, in order to form a black column spacer, a method of dispersing bead particles serving as spacers on the front surface of a substrate has been adopted. However, in such a method, it is difficult to form a spacer to a high position, and beads are also attached to the pixel display portion, thereby deteriorating the contrast and image quality of the image. Accordingly, in order to solve these problems, a method of using a photosensitive resin composition capable of forming a step has been proposed in various ways.

Conventionally, in order to form a black column spacer, a method of dispersing bead particles serving as spacers on the front surface of a substrate has been adopted. However, in such a method, it is difficult to form a spacer to a high position, and beads are also attached to the pixel display portion, thereby deteriorating the contrast and image quality of the image. Thus, in order to solve these problems, a method using a photosensitive resin composition capable of forming a step has been proposed in various ways.

Republic of Korea Patent Publication 2013-0113998 proposes a method of forming a black column spacer having a height difference by using a photosensitive resin composition, but has a disadvantage of poor adhesion of the film.

Republic of Korea Patent Publication 2013-0113998

The present invention was devised to solve the above-mentioned conventional problems, has excellent optical density (OD) characteristics, excellent NMP elution reliability and 950nm Near-IR transmission characteristics, and uses a halftone mask (slit mask). It is an object to provide a black photosensitive resin composition capable of forming a sufficient level difference by a difference in exposure amount.

In addition, an object of the present invention is to provide a color filter including a black matrix or a black column spacer formed using the black photosensitive resin composition, and to provide a liquid crystal display device having the color filter.

The present invention to achieve the above object,

Coloring material (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a melamine-based compound and one or more compounds selected from ureaaldehyde-based compounds (E) and a solvent (F) Provided is a black photosensitive resin composition.

The present invention provides a black photosensitive resin composition for forming a step for a black matrix and a black column spacer.

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

In addition, the present invention provides a liquid crystal display device having the color filter.

According to the present invention, a black photosensitive resin having excellent optical density (OD) characteristics, excellent NMP elution reliability and 950 nm near-IR transmission characteristics, and capable of forming a step by a difference in exposure dose using a halftone mask (three mask) Compositions can be provided. In addition, by using the melamine-based or urea-aldehyde-based compound of the present invention, it gives an effect of amplifying the step formation during development, and can improve reliability by acting as a curing agent between binder resins during post-bake.

In addition, according to the present invention, it is possible to provide a color filter having improved physical properties and performance including a black matrix or black column spacer using the black photosensitive resin composition and a liquid crystal display device having the same.

The present invention is a coloring material (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), one or more compounds selected from melamine-based and ureaaldehyde-based compounds (E) and solvents (F) It provides a black photosensitive resin composition capable of forming a step, characterized in that it comprises a color filter comprising a black matrix or a black column spacer formed therefrom and a liquid crystal display device having the same and a manufacturing method therefor.

Hereinafter, each component constituting the photosensitive resin composition of the present invention will be described. However, the present invention is not limited to these components.

Coloring material (A)

The coloring material (A) includes a black pigment, carbon black (A1) and an organic pigment (A2). Carbon black (A1) as the black pigment is not particularly limited as long as it is a light-shielding pigment, and a known carbon black can be used. Carbon black (A1), which is the black pigment, may specifically include channel black, furnace black, thermal black, and lamp black. In addition, carbon black (A1), which is the black pigment, may also use carbon black coated with a resin. Since the carbon black coated with the resin has a lower conductivity than the carbon black without the resin, it can provide excellent electrical insulation when forming a black matrix or black column spacer.

The organic pigment (A2) can be applied to those commonly used in the art. When the organic pigment (A2) is used alone or in combination of two or more, it is preferable to use one capable of providing excellent electrical insulation while having an optical density similar to that of carbon black. As the organic pigment (A2), various pigments used in printing inks and inkjet inks can be used. Specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments , Isoindoline pigment, perylene pigment, perinone pigment, dioxazine pigment, anthraquinone pigment, dianthraquinonyl pigment, anthrapyrimidine pigment, anthanthrone pigment, indanthrone pigment, pravanthrone And pigments, pyranthrone pigments, and diketopyrrolopyrrole pigments.

In addition, as the black pigment, metal oxides such as perylene, lactam, aniline, silver tin alloy, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc and calcium silver, complex oxides, metal sulfides, metal sulfates, and And metal carbonates.

The coloring material (A) is preferably 5 to 60% by mass, preferably 10 to 45% by mass, based on the total solid content in the colored photosensitive resin composition. When the coloring material (A) is contained in an amount of 5 to 60% by mass based on the above criteria, even if a thin film is formed, the color density of the pixel is sufficient, and since the omission of the non-pixel portion does not decrease during development, residues are unlikely to occur desirable.

In the present invention, the total solid content in the colored photosensitive resin composition means the total content of the remaining components excluding the solvent from the colored photosensitive resin composition.

Binder resin (B)

The binder resin (B) can be applied generally used in the art, in particular, it is preferable that the binder resin (B) is a copolymer of a compound having an unsaturated carboxyl group and other monomers copolymerizable therewith. The compound having an unsaturated carboxyl group is not limited as long as it is a carboxylic acid compound having an unsaturated double bond capable of polymerization, and may be used alone or in combination of two or more.

Specific examples of the compound having an unsaturated carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; Mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as anhydrides of dicarboxylic acids and ω-carboxypolycaprolactone mono (meth) acrylates, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid, 5-norbornene-2-carboxylic acid, mono-2-((meth) acryloyloxy) ethyl phthalate, mono-2-((meth) acryloyloxy) ethyl succinate, and mixtures thereof. Can be. Among the compounds having the above-mentioned unsaturated carboxyl groups, acrylic acid and methacrylic acid are preferred because of their excellent copolymerization reactivity and solubility in a developer.

The binder resin (B) is contained in an amount of 10 to 80% by mass, preferably 10 to 70% by mass, based on the total solid content in the photosensitive resin composition. When the content of the binder resin (B) is 10 to 80% by mass based on the above criteria, the solubility in the developer is sufficient to facilitate pattern formation, and film development in the pixel portion of the exposed portion is prevented during development, so that the non-pixel portion is omitted. It is preferable because the properties are good.

Photopolymerization  Compound (C)

The photopolymerizable compound (C) is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and examples thereof include a monofunctional monomer, a bifunctional monomer, and other polyfunctional monomers. Specific examples of the monofunctional monomer include nonylphenylcarbitolacrylate, 2-hydroxy-3-phenoxypropylacrylate, 2-ethylhexylcarbitolacrylate, 2-hydroxyethylacrylate and N-vinylpyrrolid And money. Specific examples of the bifunctional monomer are 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, And bis (acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ropoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol And hexa (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Among them, a bifunctional or higher polyfunctional monomer is preferably used.

The photopolymerizable compound (C) may be used in the range of 1 to 60% by mass, preferably 5 to 50% by mass, based on the total solid content in the photosensitive resin composition. When the photopolymerizable compound (C) is in the range of 1 to 60% by mass based on the above criteria, it is preferable because the pattern properties are good.

Light polymerization Initiator (D)

The photopolymerization initiator (D) is not limited, but at least one compound selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, oxime compounds, and thioxanthone compounds It is preferred to use.

Specific examples of the acetophenone-based compound are diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1 -One, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

Examples of the benzophenone-based compound include benzophenone, 0-benzoylbenzoate methyl, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra ( Tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine-based compound are 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- 1) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Specific examples of the biimidazole-based compound are 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4 And an imidazole compound in which the phenyl group at the 4,4 ', 5'-tetraphenyl-1,2'-biimidazole or 4,4', 5,5 'position is substituted with a carboalkoxy group. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.

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

The content of the photopolymerization initiator (D) is 0.1 to 40 parts by mass, preferably 1 to 30 parts by mass, based on 100 parts by mass of the binder resin (B) and the photopolymerizable compound (C) based on the solid content. If the content of the photopolymerization initiator (D) is within the above range based on the above criteria, the black photosensitive resin composition becomes highly sensitive, and the intensity of the pixel portion formed using the composition or the smoothness on the surface of the pixel portion is good. desirable.

The present invention can use a photopolymerization initiator (D-1) together with the photopolymerization initiator. The content of the photopolymerization initiation aid (D-1) is 0.1 to 50 parts by mass, preferably 1 to 40 parts by mass, based on 100 parts by mass of the binder resin (B) and the photopolymerizable compound (C) based on the solid content. . When the amount of the photopolymerization initiation aid (D-1) used is in the above range based on the above criteria, the sensitivity of the black photosensitive resin composition becomes higher, and the productivity of the color filter formed using the composition is improved, which is preferable.

Melamine or Ureaaldehyde system  Compound (E)

The melamine-based or urea-aldehyde-based compound (E) is not limited, but it is preferable to use at least one compound selected from the group consisting of melamine-based and ureaaldehyde-based compounds.

The content of the melamine-based or urea-aldehyde-based compound is 0.1 to 20 parts by mass, preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the binder resin (B) and the photopolymerizable compound (C) based on the solid content. When the content of the melamine-based or urea-aldehyde-based compound is in the above range based on the above criteria, the black photosensitive resin composition helps to form a step when developing, and the binder resin and the bonding aid included in the composition (compound containing an epoxy group) It is preferable because the film hardness and chemical resistance are improved by improving the curing degree by heat.

Preferred examples of the melamine-based or ureaaldehyde-based compounds are as follows, but are not limited thereto.

E1 E2

E3 E4

E5

Solvent (F)

The solvent (F) is not particularly limited and various organic solvents commonly used in the art can be used. Specific examples of the solvent (F) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, and diethylene Diethylene glycol dialkyl ethers such as glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, and propylene glycol Alkylene glycol alkyl ether acetates such as monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate, alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate, benzene, toluene, xylene andAromatic hydrocarbons such as mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin And esters such as 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone. Among the above-mentioned solvents, organic solvents having a boiling point of 100 to 200 ° C can be exemplified in terms of coatability and dryness, and more preferably, alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy. Esters such as ethyl propionate and methyl 3-methoxypropionate, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionate ethyl and 3-meth And methyl oxypropionate. These solvents (F) can be used alone or in combination of two or more.

The content of the solvent (F) is 60 to 90% by mass, preferably 70 to 85% by mass, in the black photosensitive resin composition containing it. When the content of the solvent (F) is in the range of 60 to 90% by mass based on the above criteria, it is applied by a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater) and inkjet. When applied, it is preferable because the coatability becomes good.

Hereinafter, it will be described in more detail by preferred examples and comparative examples of the present invention. However, the following examples are intended to illustrate the invention and should not be understood as limiting the scope of the invention.

< Manufacturing example  1> Preparation of binder resin

A flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping lot, and a nitrogen introduction tube was prepared. On the other hand, as a monomer dropping lot, 176 g (1.00 mol) of benzyl methacrylate, 35.4 g (0.30 mol) of methacrylic acid, 82.6 g (0.70 mol) of vinyl toluene, and t-butylperoxy-2-ethylhexanoate 4 g and 40 g of propylene glycol monomethyl ether acetate was added and then stirred and prepared, and as a chain transfer agent dropping tank, 6 g of n-dodecanethiol and 24 g of PGMEA were added and stirred and prepared. Thereafter, 395 g of propylene glycol monomethyl ether acetate was introduced into the flask, and the air in the flask was replaced with nitrogen, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, the monomer and the chain transfer agent were added dropwise from the dropping lot. Dropping, while maintaining at 90 ° C., each proceeded for 2 hours, and after 1 hour, the temperature was raised to 110 ° C. to proceed for 8 hours, and a resin having a solid acid value of 70 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 21,000, and the molecular weight distribution (Mw / Mn) was 2.2.

< Manufacturing example  2> black pigment Dispersion Manufacturing example 1 to  12

Among the components listed in Table 1 below, 20 parts by mass of the coloring materials (A1, A2), dispersants (G1, G2), solvent (F1), and solvent (F2) were mixed in a container, and then a high-speed stirrer (manufactured by Shinwon Industrial Machinery, It was stirred for 2 hours at a linear speed of 5 m / s through a 0.5Hp High speed mixer). Subsequently, 40 parts by mass of the solvent (F2) was further mixed, and 0.3 mm zirconia beads were used for the transverse bead mill (Dyno Co., Ltd., ECM-Lab) at a speed of 8 m / s and a flow rate of 2 kg / min. Dispersion was performed for a period of time, and after the dispersion was completed, 12.7 parts by mass of the remaining amount of the solvent (F2) was added to prepare black pigment dispersions BK1-12.

Black pigment dispersion example
(BK1 ~ 6) Preparation Example 1
(BK1) Preparation Example 2
(BK2) Preparation Example 3
(BK3) Preparation Example 4
(BK4) Preparation Example 5
(BK5) Preparation Example 6
(BK6) Coloring pigment (A1) PBK 1.0 2.0 3.0 4.0 2.0 6.0 Coloring pigment (A2) PR149 10.0 8.0 9.0 8.0 0.0 0 PB15: 6 9.0 10.0 8.0 8.0 6.0 8.0 PR254 0.0 0.0 0.0 0.0 0.0 0.0 PR177 0.0 0.0 0.0 0.0 0.0 0.0 organic black 0.0 0.0 0.0 0.0 12.0 6.0 Pigment Dispersant (G1) 0.3 0.3 0.3 0.3 0.3 0.3 Pigment Dispersant (G2) 4 4 4 4 4 4 Solvent (F1) 3 3 3 3 3 3 Solvent (F2) 72.7 72.7 72.7 72.7 72.7 72.7 Black pigment dispersion example
(BK7 ~ 12) Preparation Example 7
(BK7) Preparation Example 8
(BK8) Preparation Example 9
(BK9) Preparation Example 10
(BK10) Preparation Example 11
(BK11) Preparation Example 12
(BK12) Coloring pigment (A1) PBK 0.0 5.0 2.0 2.0 4.0 4.0 Coloring pigment (A2) PR149 14.0 6.0 4.0 14.0 0.0 0.0 PB15: 6 6.0 9.0 14.0 4.0 8.0 8.0 PR254 0.0 0.0 0.0 0.0 8.0 0.0 PR177 0.0 0.0 0.0 0.0 0.0 8.0 organic black 0.0 0.0 0.0 0.0 0.0 0.0 Pigment Dispersant (G1) 0.3 0.3 0.3 0.3 0.3 0.3 Pigment Dispersant (G2) 4 4 4 4 4 4 Solvent (F1) 3 3 3 3 3 3 Solvent (F2) 72.7 72.7 72.7 72.7 72.7 72.7

<Detailed description of ingredients used in Table 1 above>

Coloring material (A)

-PBK: Carbon Black (MA-8, manufactured by Mitsubishi Corporation)

-PR179: Pigment Red 149 (PV FAST RED B, manufactured by Clariant)

-PR254: Pigment Red 254 (BT-CF, manufactured by Ciba)

-PR177: Pigment Red 177 (manufactured by ATY-TR. DIC)

-PY15: 6: Pigment Blue 15: 6 (EP-193, manufactured by DIC)

-organic black: Pigment Black 100 (Igraphor CF100, manufactured by BASF)

Pigment Dispersant (G1): Solsperse 5000 (manufactured by Lubrisol)

Pigment Dispersant (G2): Disperbyk-163 (manufactured by BYK chemi)

Solvent (F1): n-butanol

Solvent (F2): Propylene glycol monomethyl ether acetate

< Example  1 to 6>

The coloring photosensitive resin composition was prepared by a conventional method known in the art with the composition of Table 2 below, including the binder resin prepared in the above Preparation Example. The units in Table 2 below are parts by weight.

division Parts by weight Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Black pigment dispersion (BK) 70.00 BK1 BK2 BK3 BK4 BK5 BK6 Binder resin (B) 5.00 Preparation Example 1 Binder Resin Photopolymerizable compound (C) 5.00 Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) Photopolymerization initiator (D) 1.00 Ethanone-1- [9-ethyl-6- (2-methyl-4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02; Shivasa Produce) Melamine or
Ureaaldehyde (E) 0.5 E1 E2 E3 E4 E5 E1 Solvent (F) 17.95 Propylene glycol monomethyl ether acetate Additive (H1) 0.50 Epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Kagaku Kogyo Co., Ltd.) Additive (H2) 0.05 3-methacryloxypropyltrimethoxysilane

E1 E2

E3 E4

E5

< Comparative example  1 to 8>

A colored photosensitive resin composition was prepared with the composition shown in Table 3 in the same manner as in the above Example. The units in Table 3 below are parts by weight.

division Parts by weight Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Black pigment dispersion (BK) 70.00 BK7 BK8 BK9 BK10 BK11 BK12 Binder resin (B) 5.00 Preparation Example 1 Binder Resin Photopolymerizable compound (C) 5.00 Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) Photopolymerization initiator (D) 1.00 Ethanone-1- [9-ethyl-6- (2-methyl-4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02; Shivasa Produce) Solvent (F) 18.45 Propylene glycol monomethyl ether acetate Additive (F1) 0.50 Epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Kagaku Kogyo Co., Ltd.) Additive (F2) 0.05 3-methacryloxypropyltrimethoxysilane

< Experimental Example  1> Preparation of colored substrate

The 2 square inch glass substrate (manufactured by Corning, # 1737) was washed sequentially with a neutral detergent, water and alcohol, and then dried. The black photosensitive resin composition according to the above Examples and Comparative Examples was exposed on this glass substrate at an exposure amount of 365 mJ / cm 2 (365 nm) and spin-coated so that the film thickness after firing after the development process was 1.0 μm. Then, it was pre-dried at 100 ° C for 3 minutes in a clean oven. After cooling, the substrate coated with the black photosensitive resin composition was irradiated with an exposure amount of 100 mJ / cm 2 (365 nm) in an atmospheric atmosphere using an ultra-high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd. Then, it was fired after 30 minutes at 220 ° C.

< Experimental Example  2> Optical density ( OD )

The optical density of the substrate prepared in the above Experimental Example was measured using an optical density measuring instrument (manufactured by Exlight Inc.) and the measurement results are shown in Table 4. In general, the higher the numerical value, the better the optical density.

< Experimental Example  3> Near - IR  Transmission characteristics

The substrate prepared in the experimental example was measured using a near-infrared spectroscopy equipment (VERTEX80 FT-IR spectrometer, manufactured by Bruker Optics), and the transmittance at 950 nm was measured and the measured results are shown in Table 4. In order to recognize the alignment key of the exposure machine, the transmittance of 950nm wavelength is required to be 30% or more.

< Experimental Example  4> Reliability

The substrate prepared in the above example was immersed in NMP (N-Methyl-2-pyrrolidone) and heated at 100 degrees for 30 minutes to measure the thickness change before and after the film. It is shown in Table 4 by applying the following NMP resistance evaluation criteria.

< NMP  Immunity evaluation criteria>

O: 98% or more

△: 95% to 98%

X: 95% or less

< Experimental Example  5> Adhesion

The substrate of the above example was fabricated in the same manner as in the step formation evaluation by using the LS mask (line / space = 1: 1) and irradiated with a microscope in the same manner as the step formation evaluation. It is shown in 4.

< Experimental Example  6> Step formation

A black photosensitive resin composition was applied and pre-dried using the same method as in the preparation of the colored substrate. At this time, the coated substrate was prepared so that the film thickness after firing after omitting the developing process was 3.0 µm. The photosensitive resin layer was selectively irradiated with ghi rays through a 100% transmissive portion and a negative mask capable of realizing 15% halftone. The exposure amount was 5 to 50 mJ / cm 2. Subsequently, a black column spacer was formed by spray development at 23 ° C. for 70 seconds using a 0.03 mass% KOH aqueous solution. Then, it was fired after 30 minutes at 220 ° C.

Table 4 shows the results of measuring the difference in height between the black column spacers of the 100% permeable portion and the 15% halftone portion after firing.

division Baseline Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 OD / um 1.5 or higher 1.62 1.69 1.78 1.81 1.67 1.58 Near-IR transmission 30% or more 78% 52% 40% 31% 57% 57% Step formation 0.6um or more 0.7 1.5 1.3 1.2 1.5 1.8 responsibility - O O O O O O Adhesion (L / S) - 15㎛ 15㎛ 15㎛ 15㎛ 15㎛ 10㎛ division Baseline Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 OD / um 1.5 or higher 1.40 1.83 1.30 1.45 1.20 1.03 Near-IR transmission 30% or more 89% 20% 63% 65% 31% 35% Step formation 0.6um or more 0.2 0.4 0.5 0.3 0.3 0.5 responsibility - X X X △ △ X Adhesion (L / S) - 20㎛ 25㎛ 20㎛ 15㎛ 20㎛ 15㎛

The black photosensitive resin composition of the present invention had an optical density of 1.5 or more, and a near-IR transmission property of 30% or more.

Further, according to Table 4, the black photosensitive resin composition of the present invention showed a step difference of 0.6 µm or more as a reference value in the exposure process using a halftone mask, whereas the composition of the comparative example showed a value of less than 0.6 µm. It can be seen that silver provides a black photosensitive resin composition capable of forming a sufficient level.

In addition, since the reliability test results using NMP show excellent reliability with little elution to NMP, the composition of the present invention can be usefully used for manufacturing color filters and liquid crystal displays having improved physical properties or performance.

Claims (8)

Containing at least one compound (E) and a solvent (F) selected from coloring materials (A), binder resins (B), photopolymerizable compounds (C), photopolymerization initiators (D), melamine-based and ureaaldehyde-based compounds As a black photosensitive resin composition,
Using a halftone mask, it is possible to form a step by the difference in exposure dose,
The step is 0.6㎛ or more,
The melamine-based and urea-aldehyde-based compounds, characterized in that selected from the following E1 to E5, black photosensitive resin composition.

E1 E2

E3 E4

E5 The method according to claim 1,
The coloring material (A) is a black photosensitive resin composition, characterized in that it comprises a carbon black (A1) and an organic pigment (A2). delete The method according to claim 1,
The at least one compound (E) selected from the melamine-based and urea-aldehyde-based compounds comprises 0.1 to 20 parts by mass based on 100 parts by mass of the binder resin and the photopolymerizable compound based on solid content. Photosensitive resin composition. delete The method according to claim 1,
The photosensitive resin composition is a black photosensitive resin composition, characterized in that it comprises 5 to 60 mass% of a coloring material, 10 to 80 mass% of a binder resin, and 1 to 60 mass% of a photopolymerizable compound based on solid content in the composition. A color filter comprising a black matrix or a black column spacer prepared by the black photosensitive resin composition of claim 1. A liquid crystal display device comprising the color filter according to claim 7.