TW201839063A - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

Provided are a photosensitive resin composition including (A) a black colorant including a red pigment, a blue pigment, and a violet pigment; (B) a binder resin; (C) a photopolymerizable monomer; (D) a photopolymerization initiator; and (E) a solvent, wherein the blue pigment includes a phthalocyanine-based compound having a [beta]-type crystal and a phthalocyanine-based compound having a [epsilon]-type crystal, a photosensitive resin layer manufactured using the same, and a color filter including the photosensitive resin layer.

Description

Photosensitive resin composition, photosensitive resin layer using the same, and filter

The present invention relates to a photosensitive resin composition, a photosensitive resin layer using the same, and an optical filter.

It is necessary for the photosensitive resin composition to be used in a display device (such as a filter, a liquid crystal display material, an organic light emitting diode, or a display panel material). For example, filters such as color liquid crystal displays require a black matrix at the border between colored layers (such as red, green, blue, etc.) to enhance display contrast or color development. The light blocking layer may be mainly formed of a photosensitive resin composition.

Recently, an attempt has been made to use a black matrix material as a columnar spacer supporting two TFTs having a liquid crystal layer and a C / F substrate therebetween, and such a columnar spacer is called a black columnar spacer.

The black columnar spacer should include a patterned step formed by the difference in the transmittance of the mask, and have the light blocking characteristics that function as a general black matrix, and the compressive displacement, elastic recovery rate, and breaking strength that function as a columnar spacer, and therefore have Sufficiently high optical density. In addition, since the black columnar spacer is composed of a columnar spacer and a black matrix layer at the same time, a step between a relatively high columnar spacer and a relatively low black matrix should be achieved by using a halftone mask. Unlike general black matrices, black columnar spacers directly contact liquid crystals, and necessarily require reliability features that can minimize liquid crystal contamination, and chemical resistance against polyimide solvents used as upper layers and reprocessing solutions.

However, the conventional photosensitive resin composition for a black columnar spacer still has problems of extremely narrow proper developing portions and deterioration of elution resistance against a polyimide solvent.

Therefore, research into developing a photosensitive resin composition for use in a black columnar spacer has been carried out in consideration of the above characteristics.

One embodiment of the present invention provides a photosensitive resin composition having improved chemical resistance and reliability against liquid crystal elution.

Another embodiment of the present invention provides a photosensitive resin layer manufactured using the photosensitive resin composition.

Still another embodiment of the present invention provides an optical filter including the photosensitive resin layer.

An embodiment of the present invention provides a photosensitive resin composition including (A) a black colorant, the black colorant including a red pigment, a blue pigment, and a purple pigment; (B) a binder resin; (C) a photopolymer (D) a photopolymerization initiator; and (E) a solvent, wherein the blue pigment includes a phthalocyanine-based compound having β-type crystals and a phthalocyanine-based compound having ε-type crystals.

The content of the phthalocyanine-based compound having β-type crystal may be the same as or larger than that of the phthalocyanine-based compound having ε-type crystal.

The content of the phthalocyanine-based compound having β-type crystal may be larger than that of the phthalocyanine-based compound having ε-type crystal.

The phthalocyanine-based compound having a β-type crystal may include C.I. pigment B15: 3, C.I. pigment B15: 4, or a combination thereof.

The phthalocyanine-based compound having an ε-type crystal may include a C.I. pigment B15: 6.

The red pigment may include a pyrrolopyrrole dione pigment, a perylene pigment, an anthraquinone pigment, a dianthraquinone pigment, an azo pigment, a diazo pigment, a quinacridone pigment, an anthracene pigment Or a combination.

The red pigment can be represented by Chemical Formula 1. [Chemical Formula 1] In Chemical Formula 1, R ¹ to R ^{4 are} independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C10 alkyl group, and n1 and n2 are independently integers ranging from 1 to 5.

The purple pigment can be represented by Chemical Formula 2. [Chemical Formula 2]

The black colorant may further include an orange pigment, a yellow pigment, or a combination thereof.

The adhesive resin may include a cardo-based adhesive resin.

The photosensitive resin composition may include (A) a black colorant in an amount of 1 to 15% by weight; (B) a binder resin in an amount of 1 to 10% by weight based on the total amount of the photosensitive resin composition; and 0.1% by weight. % To 10% by weight (C) of the photopolymerizable monomer; 0.1% to 5% by weight of the (D) photopolymerization initiator; and the balance of the (E) solvent.

The photosensitive resin composition may further contain additives such as malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof.

Another embodiment of the present invention provides a photosensitive resin layer manufactured using the photosensitive resin composition.

The photosensitive resin layer may be a black columnar spacer.

Another embodiment of the present invention provides an optical filter including the photosensitive resin layer.

Other embodiments of the present invention are included in the following specific implementations.

A black columnar spacer having excellent chemical resistance and reliability in a liquid crystal, and a filter including the black columnar spacer can be realized by using a photosensitive resin composition according to an embodiment.

Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, and the present invention is not limited thereto and the present invention is defined by the scope of the patent application scope.

In this specification, when no specific definition is provided otherwise, "substituted" means that at least one hydrogen atom of a compound is replaced with the following substituents: a halogen atom (F, Cl, Br, I), a hydroxyl group, C1 to C20 Alkoxy, nitro, cyano, amine, imino, azido, formamyl, hydrazine, hydrazino, carbonyl, carbamoyl, thiol, ester, ether, carboxyl, or Its salt, sulfonic acid or its salt, phosphoric acid or its salt, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C30 aryl, C3 to C20 cycloalkyl, C3 to C20 ring Alkenyl, C3 to C20 cycloalkynyl, C2 to C20 heterocycloalkyl, C2 to C20 heterocycloalkenyl, C2 to C20 heterocycloalkynyl, or a combination thereof.

In this specification, when a specific definition is not provided otherwise, "heterocycloalkyl", "heterocycloalkenyl", "heterocycloalkynyl" and "heterocycloalkyl" refer to cycloalkyl, Cyclic compounds of cycloalkenyl, cycloalkynyl and cycloalkylenes have at least one heteroatom of at least one N, O, S or P.

In this specification, when a specific definition is not provided otherwise, "(meth) acrylate" means "acrylate" and "methacrylate".

The black columnar spacer functions as a columnar spacer having a light blocking region having a sufficiently high optical density (OD) for maintaining a cell gap. In order to pattern the black columnar spacer, various black colorants can be coated on it, but various colorants (such as red pigment, orange pigment, yellow pigment, blue pigment, purple pigment, etc.) can be mixed to achieve black And therefore increase step boundaries and control reliability.

However, the black columnar spacer necessarily requires the use of a phthalocyanine-based blue pigment to ensure sufficient optical density (OD), and a blue pigment having ε-type crystals, which is most commonly used among the blue pigments, contaminates the liquid crystal And mainly cause its work problems. However, one embodiment of the present invention uses a blue pigment having a β-type crystal that is more stable than an ε-type crystal, and thus can provide a black columnar spacer having excellent solvent resistance to NMP and high reliability in liquid crystal .

Each component is specifically described below.

(A) Black colorant

The photosensitive resin composition according to an embodiment includes a black colorant including a red pigment, a blue pigment, and a purple pigment.

The blue pigment contains a phthalocyanine-based compound such as a copper phthalocyanine-based compound in order to ensure sufficient optical density, and the copper phthalocyanine-based compound includes a copper phthalocyanine-based compound having β-type crystals and a copper phthalocyanine-type having ε-type crystals Compound.

Generally, when pigments showing various colors are mixed to achieve black, copper phthalocyanine compounds having ε-type crystals are used as blue pigments, but metal ions (Cu) in copper phthalocyanine compounds having ε-type crystals It mainly pollutes liquid crystals and prevents them from working. The photosensitive resin composition according to an embodiment uses a copper phthalocyanine-based compound having β-type crystals and a copper phthalocyanine-based compound having ε-type crystals as blue pigments and thus improves chemical resistance and reliability in liquid crystal, And, therefore, the problem of reliability degradation due to liquid crystal contamination of a conventional composition prepared by using a copper phthalocyanine compound having an ε-type crystal is solved. The structure of a copper phthalocyanine compound having a β-type crystal is more stable than that of a copper phthalocyanine compound having an ε-type crystal, and therefore the phase change to an organic solvent is small and therefore does not elute well therein, and therefore, when it will When a copper phthalocyanine compound of a type crystal is used together with a copper phthalocyanine compound having a β type crystal, high reliability in liquid crystal can be achieved by controlling elution resistance. In other words, even when a phthalocyanine compound is conventionally used as a blue pigment in a mixed black colorant, a phthalocyanine compound having an ε-type crystal or a phthalocyanine compound having a β-type crystal is used alone without mixing, but one The examples solve conventional problems by mixing a phthalocyanine-based compound having an ε-type crystal and a phthalocyanine-based compound having a β-type crystal.

Specifically, the content of the phthalocyanine-based compound having β-type crystal may be the same as or larger than that of the phthalocyanine-based compound having ε-type crystal. More specifically, the phthalocyanine-based compound having a β-type crystal may be contained in a larger amount than the phthalocyanine-based compound having an ε-type crystal. In this case, chemical resistance and reliability in the liquid crystal can be further improved.

For example, the phthalocyanine compound having a β-type crystal may include C.I. pigment B15: 3, C.I. pigment B15: 4, or a combination thereof.

For example, a phthalocyanine compound having an ε-type crystal may include a C.I. pigment B15: 6.

The red pigment may include a pyrrolopyrrole dione pigment, a perylene pigment, an anthraquinone pigment, a dianthraquinone pigment, an azo pigment, a diazo pigment, a quinacridone pigment, an anthracene pigment, or a combination thereof .

For example, a red pigment may be represented by Chemical Formula 1. [Chemical Formula 1] In Chemical Formula 1, R ¹ to R ^{4 are} independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C10 alkyl group, and n1 and n2 are independently integers ranging from 1 to 5.

For example, a purple pigment can be represented by Chemical Formula 2. [Chemical Formula 2] .

When the black colorant contains a purple pigment, the transmittance in both the short-wavelength region and the visible light region is reduced compared to a black colorant that does not include a purple pigment, and in this document, because the transmittance in the visible light region is greater than The transmittance in the short-wavelength region, the optical density that is an intrinsic characteristic of the black columnar spacer, can be ultimately maximized by minimizing the loss of transmittance in the short-wavelength region and at the same time reducing the transmittance in the visible light region.

The amount of the purple pigment may be smaller than the amount of the red pigment. Here, not only the transmittance in the short-wavelength region can be ensured, but also the optical density can be increased compared to the case where a purple pigment is contained more than a red pigment.

The black colorant may further include an orange pigment, a yellow pigment, or a combination thereof.

The pigment of the black colorant may be contained in the photosensitive resin composition in the state of a pigment dispersion. Such a pigment dispersion liquid may be composed of a solid pigment, a solvent, a dispersant, a dispersion resin, and the like.

The solid pigment may be present in an amount of 1 to 20% by weight (for example, 8 to 20% by weight, such as 8 to 15% by weight, such as 10 to 20% by weight, such as 10) based on the total amount of the pigment dispersion. (% To 15% by weight) is included.

The solvent may be ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, and the like, and preferably propylene glycol Methyl ether acetate.

The dispersant facilitates uniform dispersion of the pigment, and may contain a nonionic, anionic, or cationic dispersant. Specific examples may be polyalkylene glycols or their esters, polyoxyalkylenes, polyol ester alkylene oxide addition products, alcohol alkylene oxide addition products, sulfonates, sulfonates, carboxylic acid esters, carboxylic acid salts, Alkylamine amine alkylene oxide addition products, alkylamines, and can be used alone or in the form of a mixture of two or more.

Examples of commercially available dispersants may include DISPERBYK-101, DISBBY-130, DISBBY-140, DISB, manufactured by BYK Co., Ltd. BICK-160, DISBIK-161, DISBIC-162, DISBIC-163, DISBIC-164, DISBIC-165, DISBIC-166, DISBIC -170, Disco-171, Disco-182, Disco-2000, Disco-2001; Efka (manufactured by EFKA Chemicals Co.) EFKA) -47, Efka-47EA, Efka-48, Efka-49, Efka-100, Efka-400, Efka-450; Zeneka Co. Manufactured Solsperse 5000, Sospers 12000, Sospers 13240, Sospers 13940, Sospers 17000, Sospos 20000, Sospos 24000GR, Sospos 27000, Sospos 28000, etc. Etc .; or PB711, PB821, etc. manufactured by Ajinomoto Inc.

The dispersant may be included in an amount of 0.1 to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant is included in the range, the composition has excellent stability, developability, and pattern forming ability during manufacturing of the black columnar spacer due to improved dispersion characteristics.

The dispersing resin may be an acrylic fluorene-based resin containing a carboxyl group, and improves the stability of the pigment dispersion liquid and the pattern characteristics of the pixels.

Pigments can be pretreated with water-soluble inorganic salts and humectants. When the pigment is pretreated, the average particle diameter of the pigment can become finer.

The pretreatment may be performed by kneading the pigment with a water-soluble inorganic salt and a humectant and then filtering and washing the kneaded pigment.

Kneading may be performed at a temperature of 40 ° C to 100 ° C, and filtration and washing may be performed by filtering the pigment after washing off the inorganic salt with water or the like.

Examples of the water-soluble inorganic salt may be, but are not limited to, sodium chloride, potassium chloride, and the like. Wetting agents can uniformly mix pigments with water-soluble inorganic salts and pulverize. Examples of wetting agents include alkanediol monoalkyl ethers and alcohols, alkanediol monoalkyl ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and the like, alcohols such as ethanol, isopropyl Alcohols, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol polyethylene glycol, and the like. These can be used singly or as a mixture of two or more.

The average particle size of the kneaded pigment may range from 5 nm to 200 nm, such as 5 nm to 150 nm. When the average particle diameter of the pigment is within the range, the stability of the pigment dispersion liquid can be improved without degrading the pixel resolution.

Referring to the pigment dispersion liquid based on the total amount of the photosensitive resin composition, the black colorant may be included in an amount of 1 to 15% by weight (for example, 5 to 10% by weight). For example, referring to the solids based on the total amount of the photosensitive resin composition, the black colorant may be included in an amount of 0.1 to 5% by weight (for example, 0.15 to 2.25% by weight). When the black colorant in the range is included, excellent blackness and reliability can be achieved.

(B) Adhesive resin

The photosensitive resin composition according to an embodiment includes a binder resin. The adhesive resin may further include a cardo-based adhesive resin. The card-type adhesive resin can improve the heat resistance and chemical resistance of the photosensitive resin composition.

The weight average molecular weight of the card-type adhesive resin may be 1,000 g / mol to 50,000 g / mol, and specifically 3,000 g / mol to 35,000 g / mol. When the weight average molecular weight of the card-type binder resin is within the range, excellent patternability and developability can be obtained during the manufacture of the black columnar spacer.

The card-type adhesive resin may be a compound containing a repeating unit represented by Chemical Formula 3. [Chemical Formula 3] In Chemical Formula 3, R ₂₄ to R _{27 are the} same or different, and are a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C20 alkyl group, R ₂₈ and R _{29 are the} same or different, and are a hydrogen atom or CH ₂ OR _a (R _a is vinyl, acrylate or methacrylate), R ₃₀ is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, an acrylate group or a methacrylate group, Z ₁ is a single _{bond, O, CO, SO 2,} CR b R c, SiR d R e ( wherein, R _b to R _e are the same or different, and are hydrogen An atom or a substituted or unsubstituted C1 to C20 alkyl group), or a group derived from a compound represented by Chemical Formula 4 to Chemical Formula 14, and Z ₂ is an acid anhydride residue or an acid dianhydride residue. [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] In Chemical Formula 8, R _f is a hydrogen atom, ethyl, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH = CH ₂ or phenyl. [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14]

Specifically, the card-type binder resin can be obtained by reacting a compound represented by Chemical Formula 15 with a tetracarboxylic dianhydride. [Chemical Formula 15]

The tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic dianhydride may be pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4-biphenyltetracarboxylic dianhydride , 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether Tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylhydrazone tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9 , 10-fluorene tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, and the like, but are not limited thereto.

The binder resin may be included in an amount of 1 to 10% by weight (for example, 3 to 8% by weight) based on the total amount of the photosensitive resin composition. When the binder resin in the range is included, during the manufacture of the black columnar spacer, patternability, processability, and developability are improved due to proper viscosity.

(C) Photopolymerizable monomer

The photopolymerizable monomer may be a monofunctional or polyfunctional ester compound of (meth) acrylic acid having at least one ethylenically unsaturated double bond.

The photopolymerizable monomer can cause sufficient polymerization due to an ethylenically unsaturated double bond during exposure of the pattern forming process, and thus can provide a pattern with improved heat resistance, light resistance, and chemical resistance.

Specific examples of the photopolymerizable monomer may be ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (methyl) ) Acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (Meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) Acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol mono Methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri (meth) acrylic acid ethoxyethyl phosphate, aldehyde epoxy (meth) acrylate, and the like.

Commercially available products of photopolymerizable monomers are as follows. (Meth) acrylic esters of monofunctional may comprise Toagosei Chemical Industry Co. (Toagosei Chemistry Industry Co., Ltd.) Ani Alex ^{(Aronix) M-101 ®,} M-111 ® M-114 and ^®; Nippon Kayaku Co., Ltd. (Nippon Kayaku Co., Ltd.) Kaya rad (KAYARAD) TC-110S ^® and TC-120S ^®; Osaka Organic Chemical industry Ltd. (Osaka Organic Chemical Ind, Ltd.. ) V-158 ^® and V-2311 ^® etc. Examples of the difunctional ester of (meth) acrylic acid may include Tony Synthetic Chemical Industries, Ltd.'s M-210 ^® , M-240 ^® and M-6200 ^® ; Kayarad HDDA of Nippon Kayaku Co., Ltd. ^® , HX-220 ^® , R-604 ^® ; V-260 ^® , V-312 ^® and V-335 HP ^{® of} Osaka Organic Chemical Industry Co., Ltd., etc. Examples of the trifunctional ester of (meth) acrylic acid may include Tony Synthetic Chemical Industries, Ltd.'s M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , M-7100 ^® , M -8030 ^® and M-8060 ^® ; Kayalad TMPTA ^® , DPCA-20 ^® , DPCA-30 ^® , DPCA-60 ^® and DPCA-120 ^{® of} Nippon Kayaku Co., Ltd .; V of Osaka Organic Chemical Industry Co., Ltd. -295 ^® , V-300 ^® , V-360 ^® , V-GPT ^® , V-3PA ^® , V-400 ^® and so on.

These can be used singly or as a mixture of two or more.

The photopolymerizable monomer compound may be treated with an acid anhydride to improve developability.

The photopolymerizable monomer may be included in an amount of 1% to 10% by weight (for example, 1% to 5% by weight) based on the total amount of the photosensitive resin composition. When a photopolymerizable monomer in the range is included, the photopolymerizable monomer is sufficiently cured during exposure during pattern formation, and thus improves reliability and developability using an alkaline developer.

(D) Photopolymerization initiator

The photopolymerization initiator may be a photopolymerization initiator generally used in a photosensitive resin composition, and may be, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, or a triazine-based compound. Compounds, oxime compounds, or combinations thereof.

Examples of the acetophenone-based compound may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylacetophenone, p-tert-butyl Trichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (Methylthio) phenyl) -2- (N-morpholinyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4- (N-morpholinyl) phenyl ) -Butan-1-one and so on.

Benzophenones can be benzophenone, benzophenone benzoate, benzophenethyl methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone , 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4 ' -Dichlorobenzophenone or 3,3'-dimethyl-2-methoxybenzophenone.

The thioxanthone compound may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, or 2 -Chlorothioxanthone.

The benzoin compounds may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal and the like.

The triazine compound may be 2,4,6-trichloro-s-triazine, 2-phenyl4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'- Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloro (Methyl) -s-triazine, 2-biphenyl-4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphthyl-1-methyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl-1-methyl) -4,6- Bis (trichloromethyl) -s-triazine, 2--4-trichloromethyl (sunfloweryl) -6-triazine, 2--4-trichloromethyl (4'-methoxystyryl) -6-triazine and so on.

The oxime compound may be an O-fluorenyl oxime compound, 2- (O-benzylidene oxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- ( O-acetamidoxime) -1- [9-ethyl-6- (2-methylbenzyl) -9H-oxazol-3-yl] ethanone, O-ethoxycarbonyl-α-oxyl Amino-1-phenylpropan-1-one and the like. Specific examples of the O-fluorenyl oxime may be 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl- Phenyl) -but-1-one, 1- (4-phenylthiophenyl) -butane-1,2-dione-2-oxime-O-benzoate, 1- (4-phenylthio Phenyl) -octane-1,2-dione-2-oxime-O-benzoate, 1- (4-phenylthiophenyl) -oct-1-oneoxime-O-acetate , 1- (4-phenylthiophenyl) -butan-1-oneoxime-O-acetate, and the like.

In addition to the photopolymerization initiator, an oxazole-based compound, a diketone-based compound, a fluorenyl borate compound, a diazonium-based compound, a biimidazole-based compound, a fluorene-based compound, or the like can be used as the photopolymerization initiator.

The photopolymerization initiator may be included in an amount of 0.1% to 5% by weight (for example, 0.1% to 3% by weight) based on the total amount of the photosensitive resin composition. When a photopolymerization initiator in the range is included, photopolymerization can be sufficiently performed during exposure of a patterning process for manufacturing a black columnar spacer, thereby achieving excellent sensitivity and improving transmittance.

(E) Solvent

The solvent is not particularly limited, but specifically, for example, alcohols such as methanol, ethanol, etc .; ethers such as dichloroethyl ether, n-butyl ether, diisopentyl ether, methylphenyl ether, tetrahydrofuran, etc .; glycol ethers, Such as ethylene glycol methyl ether, ethylene glycol ether, propylene glycol methyl ether, etc .; Cellosolve acetate Cellosolve methyl acetate, Cellosolve ethyl acetate, Cellosolve diethyl acetate, etc. Alcohols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether , Diethylene glycol diethyl ether, etc .; propylene glycol alkyl ether acetates, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc .; aromatic hydrocarbons, such as toluene, xylene, etc .; ketones, such as methyl formaldehyde Ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl n-butyl ketone, methyl-n-pentyl ketone, 2-heptanone Etc .; saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc .; alkyl lactates, such as methyl lactate, ethyl lactate, and the like; alkyl glycolates, such as Hydroxyl Methyl ester, ethyl hydroxyacetate, butyl glycolate, etc .; alkoxyalkyl acetates, such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate Esters, ethoxyethyl acetate, etc .; alkyl 3-hydroxypropionate, such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, etc .; alkyl 3-alkoxypropionate, such as 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc .; alkyl 2-hydroxypropionate, such as Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, etc .; alkyl 2-alkoxypropionates, such as methyl 2-methoxypropionate, 2-methyl Ethyloxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc .; alkyl 2-hydroxy-2-methylpropionate, such as 2-hydroxy-2-methyl Methyl propionate, ethyl 2-hydroxy-2-methylpropionate, etc .; alkyl 2-alkoxy-2-methylpropionate, such as methyl 2-methoxy-2-methylpropionate Esters, 2-ethoxy-2-methylpropionate, etc .; esters, such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, 2- Hydroxy-3-methyl butyrate Etc .; or ketoesters, such as ethyl pyruvate, etc., and additionally, high boiling point solvents, such as N-methylformamide, N, N-dimethylformamide, N-methylformamidine Aniline, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylarsine, benzylethyl ether, dihexyl ether, acetoacetone, isophor Isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, cellosolve phenyl acetate, and the like, and these can be used alone or in the form of a mixture of two or more.

In view of miscibility and reactivity, glycol ethers such as ethylene glycol monoethyl ether and the like can be preferably used; ethylene glycol alkyl ether acetates such as cellosolve ethyl acetate and the like; esters such as propionic acid 2-hydroxyethyl etc .; diethylene glycol, such as diethylene glycol monomethyl ether, etc .; or propylene glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc. .

The solvent is used in the balance (for example, 50 to 90% by weight) based on the total amount of the photosensitive resin composition. When a solvent in the range is included, the coating characteristics of the photosensitive resin composition are improved, and excellent flatness of a film having a thickness of 3 μm or more can be maintained.

(F) Other additives

The photosensitive resin composition may further include additives such as malonic acid; 3-amino-1,2-propylene glycol; a silane-based coupling agent containing a vinyl group or a (meth) acryloxy group; a leveling agent; a fluorine-based agent Surfactants; radical polymerization initiators, etc. to prevent staining or specks during coating, adjust flatness, or prevent pattern residues due to undeveloped.

Examples of the silane-based coupling agent may be trimethoxysilylbenzoic acid, γ-methacrylfluorenylpropoxytrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-isocyanate Propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like, and these can be used alone or with Two or more mixtures are used.

Examples of the fluorine-based surfactant may be a chemical company BM (BM Chemie Inc.) The ^{BM-1000 ®, BM-1100} ® and the like; Dainippon Ink Chemical Industries, Ltd. (Dainippon Ink Kagaku Kogyo Co., Ltd. ) of MEGAFACE F 142D ^® , McFace F 172 ^® , McFace F 173 ^® , McFace F 183 ^®, etc .; Sumitomo 3M Co., Ltd. Fullerad FC-135 ^® , Fullerad FC-170C ^® , Fullerad FC-430 ^® , Fullerad FC-431 ^®, etc .; Asahi Glass Co., Ltd. ., Ltd.) SURFLON S-112 ^® , Sauron S-113 ^® , Sauron S-131 ^® , Sauron S-141 ^® , Sauron S-145 ^®, etc .; Toray Silicone Ltd. (Toray Silicone Co., Ltd.) SH-28PA ^® , SH-190 ^® , SH-193 ^® , SZ-6032 ^® , SF-8428 ^® and so on.

The other additives may be included in an amount of 0.01 to 10 parts by weight (for example, 0.01 to 5 parts by weight) based on 100 parts by weight of the photosensitive resin composition. When other additives in the range are included, close contact characteristics, storage capacity, and the like are improved.

The photosensitive resin composition may further include a predetermined amount of other additives, such as an antioxidant, a stabilizer, and the like, as long as it does not degrade characteristics.

Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition. The method of manufacturing the said photosensitive resin layer is as follows.

(1) Coating and film formation steps

The photosensitive resin composition is coated on a substrate subjected to a predetermined pretreatment using a spin or slit coating method, a roll coating method, a screen printing method, a coater method, or the like to have a desired thickness, for example, in a range of 0.9 μm to 4.0. The thickness is within a micrometer, and the coated substrate is then heated at a temperature ranging from 70 ° C to 100 ° C for 1 minute to 10 minutes to remove the solvent, thereby providing a film.

(2) Exposure steps

After placing a mask having a predetermined shape (a mask including a half-tone portion providing a black matrix pattern and a full-tone portion providing a columnar spacer pattern), the obtained film was subjected to actinic rays of 200 nm to 500 nm Radiation to form the desired pattern.

The radiation is performed by using a light source, such as a mercury lamp, a metal halide lamp, an argon laser, or the like having a low pressure, a high pressure, or an ultra high pressure, and an X-ray, an electron beam, or the like may also be used as necessary.

When using a high-pressure mercury lamp, a light dose of 500 mJ / cm2 or less (with a 365 nm sensor) can be used, but it depends on the type of each component of the photosensitive resin composition, Its combination ratio and dry film thickness, light dose can be changed.

(3) Development step

After the exposure process, the exposed film is developed using an alkaline aqueous solution by dissolving and removing unnecessary portions other than the exposed portion, thereby forming an image pattern.

(4) Post-processing steps

The developed image pattern can be reheated or cured by actinic radiation, etc., in order to achieve heat resistance, light resistance, close contact characteristics, crack resistance, chemical resistance, high strength, storage stability, etc. Excellent quality.

Examples of the present invention are described below. However, these examples should not be construed as limiting the scope of the invention in any sense.

(Preparation of photosensitive resin composition)

Examples 1 to 3 and Comparative Examples 1 and 2

The photosensitive resin compositions according to Examples 1 to 3 and Comparative Examples 1 and 2 were prepared by using the following components shown in Table 1, respectively.

Specifically, the content of the photopolymerization initiator is accurately measured and put into a solvent, and then it is sufficiently stirred until the photopolymerization initiator is completely dissolved therein (30 minutes or more). Subsequently, a binder resin and a photopolymerizable monomer were sequentially added thereto, and then they were stirred for about one hour. Next, a black colorant (pigment dispersion liquid) was added thereto, other additives were added thereto, and the entire composition obtained was finally stirred for 2 hours or more to prepare a photosensitive resin composition.

Each component used in the photosensitive resin composition is as follows. (A) Black colorant (A-1) contains CI blue pigment 15: 6 (Sanyo Ltd.) paint base dispersion (solid: 15%) (A-2) contains CI Coating dispersion (solid: 15%) of blue pigment 15: 3 (Sanyo Sanyo) (A-3) Coating dispersion (solid: 15%) containing CI purple pigment 29 (SAKATA CORP.) ( A-4) Coating dispersion (solid: 15%) containing CI red pigment 254 (ENF) (A-5) Coating dispersion (solid: 15%) containing organic black pigment (BASF Corporation) ( B) Binder Resin Card binder resin (V259ME, Nippon Steel Chemical. Co., Ltd.) (C) Photopolymerizable monomer dipentaerythritol hexa (meth) acrylate ( dipentaerythritol hexa (meth) acrylate, DPHA, Nippon Shokubai Co., LTD.) (D) Photopolymerization initiator OXE01 (BASF) (E) Solvent (E-1) Propylene glycol monomethyl ether ethyl Esters (propylene glycol monomethylether acetate, PGMEA, SIG -Sigma-Aldrich Co. LLC.) (E-2) ethylene glycol dimethyl ether (EDM, Sigma-Aldrich Co., Ltd.) (F) other additives Leveling agent (F-554, DIC Co., Ltd.) Table 1 (Unit:% by weight)

Evaluation 1: Measuring elution of metal ions

(HPLC measurement)

The photosensitive resin compositions according to Examples 1 to 3 and Comparative Examples 1 and 2 were coated on a substrate to be pretreated in advance to a thickness of 2.0 μm, and then heated at 90 ° C. for 4 minutes to remove the solvent, and thus formed membrane. Subsequently, the film was covered with a photomask, exposed with 40 mJ, and baked in a convection oven at 220 ° C for 25 minutes. Next, the film sample was cut to a size of 1.5 cm x 3.0 cm and immersed in a vial containing 10 grams of NMP. The vial was allowed to stand at 100 ° C for 60 minutes, and then NMP was collected separately. The collected NMP (eluent) was filtered by using a 0.2 micron syringe screening program and then placed in an HPLC vial to measure HPLC, and the results are shown in Table 2. The measurement was performed under the following conditions. -Column: Shiseido, Capcell pak, MGII, 4.6 mm x 250 mm, C18, 5 microns-Flow rate: 1 ml / min-Injection volume: 10 µl-Column oven temperature: 40 ° C- Analysis time: 60 minutes Table 2

Referring to Table 2, in Examples 1 to 3 including phthalocyanine compounds having β-type crystals and phthalocyanine compounds having ε-type crystals, the amount ratios of the collected organic eluents are in Comparative Example 1 and Comparative Example 2 Medium less. In addition, in Examples 1 and 2 in which the content of the phthalocyanine-based compound having a β-type crystal was larger than or equivalent to the content of the phthalocyanine-based compound having an ε-type crystal, the organic elution was compared with that in Comparative Example 1. Liquid reduction is greater than or equal to 100%.

(UV-vis measurement)

The photosensitive resin compositions according to Examples 1 to 3 and Comparative Example 1 were coated on the substrates that were pretreated in advance to 2.0 micrometers in thickness, and then heated at 90 ° C. for 4 minutes to remove the solvent, and thus a film was formed. Subsequently, the film was covered with a photomask, exposed with 40 mJ, and the substrate having the film was baked in a convection oven at 220 ° C. for 25 minutes. Next, a 0.2 gram film sample was collected and impregnated with 10 grams of liquid crystal in a vial. After the vial was maintained at 100 ° C for 60 minutes, the liquid crystal was collected separately, and the absorbance of the liquid crystal was measured by using an analytical device (Agilent Cary 5000UV-vis-NIR), and the results are shown in FIG. 1.

Referring to FIG. 1, Examples 1 to 3 using a phthalocyanine-based compound having β-type crystals and a phthalocyanine-based compound having ε-type crystals show that the peak at 671 nm is lower than that of Comparative Example 1. In addition, the amount of the phthalocyanine-based compound having β-type crystals was greater than or equal to the amount of the phthalocyanine-based compound having ε-type crystals. Examples 1 and 2 show a peak at 671 nm compared to Comparative Example 1. A sharp decline. Here, the peak at 671 nm is caused by the elution of copper phthalocyanine blue, and when this peak decreases, the photosensitive resin composition according to one embodiment has high reliability.

Assessment 2: Measuring VHR

The photosensitive resin compositions according to Examples 1 to 3 and Comparative Examples 1 and 2 were coated on an ITO patterned glass substrate to form each film. The film and the ITO patterned electrode were assembled and compressed with each other, and after the liquid crystal was injected therebetween, sealed to manufacture a device for a sample. The sample device was used to measure VHR (60 ° C and 10 Hz) by using AUtronic VHRM, and the results are shown in Table 3. table 3

Referring to Table 3, in Examples 1 to 3 using a phthalocyanine compound having β-type crystals and a phthalocyanine compound having ε-type crystals as blue pigments in a black colorant, the amount of eluted metal ions and the comparative example 1 is significantly reduced compared to Comparative Example 2, and therefore, Examples 1 to 3 finally prevent liquid crystal defects and exhibit excellent light blocking characteristics.

Although the present invention has been described in conjunction with what is presently considered as a practical example embodiment, it should be understood that the invention is not limited to the disclosed embodiments, but rather the present invention is intended to cover the spirit and scope of the scope of patents included in the attached application Various modifications and equivalent configurations within. Therefore, the foregoing embodiments should be understood as illustrative and not restrictive of the invention in any way.

no.

FIG. 1 is a graph showing absorbances according to Examples 1 to 3 and Comparative Example 1. FIG.

Claims (15)

A photosensitive resin composition comprising: (A) a black colorant, the black colorant comprising a red pigment, a blue pigment, and a purple pigment; (B) a binder resin; (C) a photopolymerizable monomer; (D) ) A photopolymerization initiator; and (E) a solvent, wherein the blue pigment includes a phthalocyanine-based compound having β-type crystals and a phthalocyanine-based compound having ε-type crystals. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the phthalocyanine-based compound having a β-type crystal contains the same amount as or larger than the phthalocyanine-based compound having an ε-type crystal. The photosensitive resin composition according to item 2 of the scope of the patent application, wherein the phthalocyanine-based compound having β-type crystals has a larger content than the phthalocyanine-based compound having ε-type crystals. The photosensitive resin composition according to item 1 of the scope of the patent application, wherein the phthalocyanine compound having a β-type crystal comprises C.I. pigment B15: 3, C.I. pigment B15: 4, or a combination thereof. The photosensitive resin composition according to item 1 of the scope of the patent application, wherein the phthalocyanine compound having an ε-type crystal contains a C.I. pigment B15: 6. The photosensitive resin composition according to item 1 of the scope of the patent application, wherein the red pigment comprises a pyrrolopyrrole dione pigment, a perylene pigment, an anthraquinone pigment, a dianthraquinone pigment, an azo pigment, Diazo pigments, quinacridone pigments, anthracene pigments, or combinations thereof. The photosensitive resin composition according to item 6 of the scope of patent application, wherein the red pigment is represented by Chemical Formula 1: [Chemical Formula 1] Wherein, in Chemical Formula 1, R ₁ to R _{4 are} independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C10 alkyl group, and n1 and n2 are independently integers ranging from 1 to 5 . The photosensitive resin composition according to item 1 of the scope of patent application, wherein the purple pigment is represented by Chemical Formula 2: [Chemical Formula 2] . The photosensitive resin composition according to item 1 of the scope of patent application, wherein the black colorant further comprises an orange pigment, a yellow pigment, or a combination thereof. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the adhesive resin further comprises a card-type adhesive resin. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the photosensitive resin composition comprises: 1% to 15% by weight (A) based on the total amount of the photosensitive resin composition The black colorant; 1% to 10% by weight (B) of the binder resin; 0.1% to 10% by weight of (C) the photopolymerizable monomer; 0.1% to 5% by weight (D) the photopolymerization initiator; and the balance (E) the solvent. The photosensitive resin composition according to item 1 of the patent application scope, wherein the photosensitive resin composition further comprises malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, and fluorine Surfactant-like, radical polymerization initiator, or a combination of additives. The photosensitive resin layer is manufactured using the photosensitive resin composition as described in any one of Claims 1-12. The photosensitive resin layer according to item 13 of the scope of patent application, wherein the photosensitive resin layer is a black columnar spacer. An optical filter includes the photosensitive resin layer according to item 13 of the scope of patent application.