KR102036684B1 - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

(A) a black colorant comprising a red pigment, a blue pigment and a violet pigment; (B) binder resin; (C) photopolymerizable monomer; (D) photoinitiator; And (E) a solvent, wherein the blue pigment comprises a photosensitive resin composition comprising a phthalocyanine-based compound having a β-type crystal and a phthalocyanine-based compound having an ε-type crystal, a photosensitive resin film prepared using the same, and a photosensitive resin film A color filter is provided.

Description

Photosensitive resin composition, photosensitive resin film and color filter using same {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE RESIN LAYER USING THE SAME AND COLOR FILTER}

The present substrate relates to a photosensitive resin composition, a photosensitive resin film, and a color filter using the same.

The photosensitive resin composition is an essential material for the production of display elements such as color filters, liquid crystal display materials, organic light emitting elements, and display panel materials. For example, a color matrix such as a color liquid crystal display requires a black matrix at a boundary between colored layers such as red, green, and blue in order to increase display contrast and color development effects. The black matrix is mainly formed of the photosensitive resin composition.

Recently, efforts have been made to use the black matrix material as a column spacer for supporting between two TFTs and a C / F substrate which exist with a liquid crystal layer interposed therebetween. The column spacer is called a black column spacer.

In the case of the black column spacer, the step difference of the pattern should be formed by the difference in the transmittance of the photo mask, and the optical density should be provided simultaneously with the compression displacement, the elastic recovery rate, and the breaking strength as well as the function of the general black matrix. Should be high enough. In addition, since the column spacer and the black matrix layer are formed at the same time, a step of a high column spacer and a relatively low black matrix must be implemented using a half tone mask. Unlike the general black matrix, the black column spacer is a layer in direct contact with the liquid crystal, and thus requires reliability characteristics to minimize liquid crystal contamination, and the chemical resistance of the solvent for the upper layer polyimide solvent and rework Is also essential.

However, the conventional photosensitive resin composition for black column spacers still has a problem in that the appropriate developing section is very narrow and the solvent resistance to the polyimide solvent is still poor.

Therefore, the research to develop the photosensitive resin composition for black column spacers which considered the above characteristics is continued.

One embodiment of the present invention is to provide a photosensitive resin composition having excellent chemical resistance and reliability of liquid crystal elution.

Another embodiment of the present invention is to provide a photosensitive resin film prepared using the photosensitive resin composition.

Another embodiment of the present invention is to provide a color filter comprising the photosensitive resin film.

One embodiment of the present invention (A) a black colorant comprising a red pigment, blue pigment and violet pigment; (B) binder resin; (C) photopolymerizable monomer; (D) photoinitiator; And (E) a solvent, wherein the blue pigment provides a photosensitive resin composition comprising a phthalocyanine compound having a β (beta) type crystal and a phthalocyanine compound having an ε (epsilon) type crystal.

The phthalocyanine-based compound having the β-type crystal may be included in an amount greater than or equal to the content of the phthalocyanine-based compound having the ε-type crystal.

The phthalocyanine-based compound having the β-type crystal may be included in a greater amount than the phthalocyanine-based compound having the ε-type crystal.

Phthalocyanine-based compound having the β-type crystals are C.I. Pigment B15: 3, C.I. Pigment B15: 4 or a combination thereof.

Phthalocyanine-based compound having the ε-type crystals are C.I. Pigment B15: 6.

The red pigment may be pyrrolopyrrole-dione pigment, perylene pigment, anthraquinone pigment, dianthraquinone pigment, azo pigment, diazo pigment, quinacridone Pigments, anthracene pigments or combinations thereof.

The red pigment may be represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

n1 and n2 are each independently an integer of 1-5.

The violet pigment may be represented by the following formula (2).

[Formula 2]

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

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

The photosensitive resin composition may comprise 1% by weight to 15% by weight of the (A) black colorant, based on the total amount of the photosensitive resin composition; 1 wt% to 10 wt% of the (B) binder resin; 0.1 wt% to 10 wt% of the (C) photopolymerizable monomer; 0.1% to 5% by weight of the photopolymerization initiator (D); And (E) may include the remaining amount of the solvent.

The photosensitive resin composition may further include additives of malonic acid, 3-amino-1,2-propanediol, a silane 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 film prepared using the photosensitive resin composition.

The photosensitive resin film may be a black column spacer.

Another embodiment of the present invention provides a color filter including the photosensitive resin film.

Other specific details of embodiments of the present invention are included in the following detailed description.

By using the photosensitive resin composition according to an embodiment, a black column spacer having excellent chemical resistance and reliability in liquid crystal and a color filter including the same may be implemented.

1 is a graph of absorbance according to Examples 1 to 3 and Comparative Example 1.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the present specification, "substituted" means that at least one hydrogen atom of the compound is a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, already Nogi group, azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof , C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocyclo Substituted with a substituent of an alkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group or a combination thereof.

Unless otherwise specified in the specification, "heterocycloalkyl group", "heterocycloalkenyl group", "heterocycloalkynyl group" and "heterocycloalkylene group" are each cycloalkyl, cycloalkenyl, cycloalkynyl and cycloalkyl. It means that at least one hetero atom of N, O, S or P is present in the ring compound of the len.

Unless otherwise specified herein, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible.

In the case of the black column spacer, the optical density (OD) has a sufficiently high light shielding portion and a column spacer for maintaining a cell gap. Various black colorants are applied to the pattern formation of such black column spacers, and blacks are mixed by mixing colorants having various colors such as red pigments, orange pigments, yellow pigments, blue pigments, and violet pigments, thereby increasing step margin and increasing reliability. Also controls.

However, in order to secure sufficient optical density (OD), black column spacers must use phthalocyanine blue pigment. Of these, the most commonly used blue pigment with ε (Epsilon) crystal is a liquid crystal. Contamination is a major cause of problems in liquid crystal driving. However, according to one embodiment, using a blue pigment having a β (beta) type crystal having a more stable crystal form than the ε (Epsilon) type crystal, a black column spacer having excellent solvent resistance to NMP and high reliability in liquid crystals Can provide.

Each component is demonstrated concretely below.

(A) black colorant

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

The blue pigment includes a phthalocyanine-based compound such as a copper-phthalocyanine-based compound to ensure sufficient optical density, and the copper-phthalocyanine-based compound includes a copper-phthalocyanine-based compound having a β-type crystal and a copper-phthalocyanine having an ε-type crystal. It includes all system compounds.

In general, when a pigment having various colors are mixed to realize black, a copper-phthalocyanine compound having an ε-type crystal is used as a blue pigment, but the metal ion (Cu) in the copper-phthalocyanine compound having the ε-type crystal is used. ) Is a major cause of liquid crystal contamination, and there is a problem that a liquid crystal driving disorder occurs. The photosensitive resin composition according to the present invention improves chemical resistance and reliability in liquid crystal by using a copper-phthalocyanine-based compound having a β-type crystal together with a copper-phthalocyanine-based compound having an ε-type crystal as the blue pigment. The problem of reliability deterioration due to liquid crystal contamination caused by using only a copper-phthalocyanine compound having an ε-type crystal was solved. Copper-phthalocyanine-based compounds having β-type crystals have a more stable structure than copper-phthalocyanine-based compounds having ε-type crystals, and thus have less phase transition to organic solvents, and thus do not elute well. When used together with a copper-phthalocyanine-based compound having a β-type crystal, high reliability in liquid crystals can be realized through solvent resistance control. That is, conventionally, even when the phthalocyanine-based compound is used as the blue pigment in the mixed black colorant, the phthalocyanine-based compound having the ε-type crystal or the phthalocyanine-based compound having the β-type crystal was used alone, but they were not mixed and used. In the embodiment, by mixing them, the conventional problem is solved.

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

For example, the phthalocyanine-based compound having the β-type crystals are C.I. Pigment B15: 3, C.I. Pigment B15: 4 or a combination thereof.

For example, the phthalocyanine compound having the ε-type crystal is C.I. Pigment B15: 6.

The red pigment may be pyrrolopyrrole-dione pigment, perylene pigment, anthraquinone pigment, dianthraquinone pigment, azo pigment, diazo pigment, quinacridone Pigments, anthracene pigments or combinations thereof.

For example, the red pigment may be represented by the following Chemical Formula 1.

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

n1 and n2 are each independently an integer of 1-5.

For example, the violet pigment may be represented by the following formula (2).

[Formula 2]

When the black colorant includes the violet pigment, both the transmittance in the short wavelength region and the transmittance in the visible light region are lower than those when the black pigment does not include the violet pigment. The greater transmittance reduction in the visible light region can minimize the loss of transmittance in the short wavelength region, while at the same time lowering the transmittance in the visible light region, thereby maximizing the optical density, which is inherent to the black column spacer.

The violet pigment may be included in a smaller amount than the red pigment. In this case, compared to the case where the violet pigment is contained in more content than the red pigment, the optical density can be increased while ensuring the transmittance in the short wavelength region.

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

Pigments constituting the black colorant may be included in the photosensitive resin composition in the form of a pigment dispersion. Such pigment dispersion may be composed of a solid pigment and a solvent, a dispersant, a dispersion resin and the like.

The pigment of the solid content is 1% to 20% by weight, such as 8% to 20% by weight, such as 8% to 15% by weight, such as 10% to 20% by weight, such as 10% by weight, based on the total amount of the pigment dispersion. It may be included in 15% by weight.

As the solvent, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, and the like can be used, and among these, propylene glycol methyl ether acetate can be used. Can be.

The dispersant helps to uniformly disperse the pigment in the dispersion, and can be used for both nonionic, anionic or cationic dispersants. Specifically, polyalkylene glycol or ester thereof, polyoxy alkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salt, alkyl amide alkylene oxide addition Water, alkyl amine, etc. can be used, These can be used individually or in mixture of 2 or more types.

Examples of commercially available products of the dispersant include, for example, DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, and DISPERBYK. -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, and the like; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. of EFKA Chemical Co., Ltd .; Zenspera Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, and the like; Or PB711, PB821 from Ajinomoto.

The dispersant may be included in an amount of 0.1 wt% to 15 wt% based on the total amount of the photosensitive resin composition. When the dispersant is included in the above range, according to the excellent dispersibility of the composition, it is excellent in stability, developability and patternability when preparing the black column spacer.

The dispersion resin may use an acrylic resin including a carboxyl group, which may not only improve the stability of the pigment dispersion but also improve the pattern of the pixel.

The pigment may be used after pretreatment using a water-soluble inorganic salt and a humectant. When the pigment is used after the pretreatment, the average particle diameter of the pigment can be refined.

The pretreatment may be performed by kneading the pigment with a water-soluble inorganic salt and a wetting agent, and filtering and washing the pigment obtained in the kneading step.

The kneading may be carried out at a temperature of 40 ° C to 100 ° C, and the filtration and washing may be performed by washing the inorganic salt with water and the like followed by filtration.

Examples of the water-soluble inorganic salts include sodium chloride and potassium chloride, but are not limited thereto. The wetting agent serves as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed so that the pigment can be easily pulverized. Examples thereof include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and the like. Alkylene glycol monoalkyl ethers; Alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol, and the like, and the like, and these may be used alone or in combination of two or more.

The pigment passed through the kneading step may have an average particle diameter of 5 nm to 200 nm, such as 5 nm to 150 nm. When the average particle diameter of a pigment is in the said range, stability in a pigment dispersion liquid is excellent and there is no fear of the resolution fall of a pixel.

The black colorant may be included in an amount of 1 wt% to 15 wt%, such as 5 wt% to 10 wt%, based on the pigment dispersion based on the total amount of the photosensitive resin composition. For example, the black colorant may be included in an amount of 0.1 wt% to 5 wt%, such as 0.15 wt% to 2.25 wt%, based on solids, based on the total amount of the photosensitive resin composition. When the black colorant is used within the above range, excellent blackness and reliability can be realized.

(B) binder resin

The photosensitive resin composition according to one embodiment includes a binder resin. The binder resin may include a cardo-based binder resin. When the cardo-based binder resin is used, heat resistance and chemical resistance of the photosensitive resin composition may be improved.

The weight average molecular weight of the cardo-based binder resin may be 1,000 g / mol to 50,000 g / mol, specifically 3,000 g / mol to 35,000 g / mol. When the weight average molecular weight of the cardo-based binder resin is within the above range, excellent patternability and developability may be obtained when the black column spacer is manufactured.

The cardo-based binder resin may be a compound including a repeating unit represented by Formula 3 below.

[Formula 3]

(In Chemical Formula 3,

R ₂₄ to R ₂₇ are the same as or different from each other, a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ₂₈ and R ₂₉ are the same as or different from each other, are a hydrogen atom or CH ₂ OR _a (R _a is a vinyl group, an acrylate group or a methacrylate group),

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 (where R _b to R _e are the same as or different from each other, a hydrogen atom, or a substituted or unsubstituted C 1 to C 20 alkyl group Is), or any one selected from compounds represented by the following Chemical Formulas 4 to 14,

Z ₂ is an acid anhydride residue or an acid dianhydride residue.)

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

(In Formula 8,

R _f is a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH═CH ₂ or a phenyl group.)

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

Specifically, the cardo-based binder resin may be obtained by reacting a compound represented by Formula 15 with tetracarboxylic dianhydride.

[Formula 15]

The tetratetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic dianhydride include 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'-biphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3 , 6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetra Carboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, and the like, but are not limited thereto.

The binder resin is based on the total amount of the photosensitive resin composition. 　 1 wt% to 10 wt%, such as 3 wt% to 8 wt%. When the binder resin is included in the above range, the viscosity is appropriately maintained to excellent patternability, processability and developability in the production of black column spacers.

(C) Photopolymerizable  Monomer

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

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, it can form a pattern excellent in heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern forming process.

Specific examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) 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) acrylic Latex, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monometh Butyl ether (meth) acrylate, trimethylol propane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate, and the like.

Examples of commercially available products of the photopolymerizable monomer are as follows. Examples of the monofunctional ester of (meth) acrylic acid include Aronix M-101 ^® , M-111 ^® , M-114 ^®, and the like manufactured by Toagosei Kagaku Kogyo Co., Ltd .; Nihon Kayaku Co., Ltd. KAYARAD TC-110S ^® , TC-120S ^®, etc .; The V-158 ^® and V-2311 ^{® of} Osaka Yuki Chemical Co., Ltd. are mentioned. Examples of the difunctional ester of the (meth) acrylic acid include, but are not limited to, Aronix M-210 ^® , M-240 ^® , M-6200 ^®, etc. manufactured by Toagosei Chemical Industries, Ltd .; Nihon Kayaku Co., Ltd. KAYARAD HDDA ^® , HX-220 ^® , R-604 ^®, etc .; And V-260 ^® , V-312 ^® and V-335 HP ^{® from} Osaka Yuki Kagaku Kogyo Co., Ltd. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -7100 ^® , M-8030 ^® , M-8060 ^®, etc .; Nippon Kayaku Co., Ltd. KAYARAD TMPTA ^® , DPCA-20 ^® , East-30 ^® , East-60 ^® , East-120 ^®, etc .; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. The above products can be used alone or in combination of two or more.

The photopolymerizable monomer may be used by treating with an acid anhydride in order to impart better developability.

The photopolymerizable monomer may be included in an amount of 0.1 wt% to 10 wt%, such as 1 wt% to 5 wt%, based on the total amount of the photosensitive resin composition. When a photopolymerizable monomer is contained in the said range, hardening arises at the time of exposure in a pattern formation process, and it is excellent in reliability, and is excellent in developability to an alkaline developing solution.

(D) Photopolymerization Initiator

The photoinitiator is a photoinitiator generally used in the photosensitive resin composition, for example, acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, or these Can be used in combination.

Examples of the acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, and pt-butyl Dichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one , 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one; and the like can be used.

Examples of the benzophenone compounds include benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, and 4,4'- Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like can be used.

Examples of the thioxanthone compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone and 2-chlorothione. Orcanthone etc. can be used.

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

Examples of the triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) -s-triazine, and 2- (3 ', 4'-dimethoxy Styryl) -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 (trichloromethyl) -s-triazine, 2- Biphenyl 4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2-4-trichloromethyl ( Piperonyl) -6-triazine, 2-4-trichloromethyl (4'-methoxystyryl) -6-triazine and the like can be used.

Examples of the oxime compounds include O-acyl oxime compounds, 2- (O-benzoyl oxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, and 1- (O-acetyl oxime)- 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, and the like. Can be used. Specific examples of the O-acyl oxime compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane- 1-one, 1- (4-phenylsulfanylphenyl) -butane-1,2-dione-2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1-one oxime-O-acetate, 1- (4-phenylsulfanylphenyl) -butane-1-one oxime- O-acetate can be used.

In addition to the above kinds of photopolymerization initiators, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, biimidazole compounds, fluorene compounds and the like can also be used as the photopolymerization initiator.

The photopolymerization initiator may be included in an amount of 0.1 wt% to 5 wt%, such as 0.1 wt% to 3 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included in the above range, the photopolymerization occurs sufficiently during exposure in the pattern forming process for manufacturing the black column spacer, so that the sensitivity is excellent and the transmittance is improved.

(E) solvent

The solvent is not particularly limited, and specific examples thereof include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butylkenone, methyl-n-amyl ketone and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate and butyl hydroxyacetate; Acetate alkoxyalkyl esters, such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate and methyl 2-hydroxy-3-methylbutanoate; Or ketone acid esters such as ethyl pyruvate, and N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid Ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like, and these may be used alone or in combination of two or more thereof.

Considering miscibility and reactivity in the solvent, glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycols such as diethylene glycol monomethyl ether; Propylene glycol alkylether acetates such as propylene glycol monomethylether acetate and propylene glycol propylether acetate can be used.

The solvent may be included in a balance, such as 50 wt% to 90 wt%, based on the total amount of the photosensitive resin composition. When a solvent is contained in the said range, the applicability | paintability of the photosensitive resin composition is excellent, and the flatness excellent in the film | membrane of 3 micrometers or more in thickness can be maintained.

(F) other additives

The photosensitive resin composition may include: malonic acid to prevent stains or spots upon application, to prevent leveling characteristics, and to prevent generation of residues due to undeveloped properties; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; It may further include other additives such as radical polymerization initiators.

Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, and γ -Glycidoxy propyl trimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl trimethoxysilane, etc. are mentioned, These can be used individually or in mixture of 2 or more types.

Examples of the fluorine-based surfactants include BM-1000 ^® , BM-1100 ^®, etc. of BM Chemie Co., Ltd .; Mecha Packs F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^®, etc. of Dai Nippon Inki Chemical Co., Ltd .; Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^®, etc. of Sumitomo 3M Co., Ltd .; Saffron S-112 ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^®, etc. of Asahi Grass Co., Ltd .; Toray silicone (Note) ^® SH-28PA of社(g), copper ^® -190, may be a commercially available product such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The other additives may be included in an amount of 0.01 to 10 parts by weight, such as 0.01 to 5 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the other additives are included in the above range, it is excellent in adhesion, shelf life and the like.

In addition, the photosensitive resin composition may be added a certain amount of other additives such as antioxidants, stabilizers, etc. within a range that does not impair the physical properties.

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

(1) application and coating film forming step

The above-mentioned photosensitive resin composition is subjected to a desired thickness, for example, from 0.9 μm to 4.0 μm, using a method such as spin or slit coating method, roll coating method, screen printing method, applicator method, etc. on a substrate subjected to a predetermined pretreatment. After coating, the coating film is formed by heating at a temperature of 70 ° C to 100 ° C for 1 to 10 minutes to remove the solvent.

(2) exposure step

In order to form a pattern required for the obtained coating film, a predetermined type of mask (a mask composed of a halftone portion to implement a black matrix pattern and a Fulton portion to implement a column spacer pattern) is interposed therebetween, and an active line of 200 nm to 500 nm is irradiated.

As a light source used for irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. can be used, and X-rays, an electron beam, etc. can also be used in some cases.

The exposure amount depends on the type, compounding amount, and dry film thickness of each component of the photosensitive resin composition, but, for example, when using a high pressure mercury lamp, 500 mJ / cm ² (Based on a 365 nm sensor).

(3) developing stage

Subsequent to the exposure step, an alkaline aqueous solution is used as a developing solution to dissolve and remove unnecessary portions, thereby remaining only the exposed portions to form an image pattern.

(4) post-processing steps

The image pattern obtained by the above development can be cured by heating again or by actinic radiation in order to obtain an excellent pattern in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, storage stability and the like.

Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

(Photosensitive resin composition production)

Example  1 to Example  3, Comparative example  1 and Comparative example  2

The photosensitive resin composition according to Examples 1 to 3, Comparative Example 1 and Comparative Example 2 was prepared using the components mentioned below in the compositions shown in Table 1 below.

Specifically, after accurately measuring the content of the photopolymerization initiator, the solvent was added, and the mixture was sufficiently stirred until the photopolymerization initiator was dissolved (at least 30 minutes). The binder resin and the photopolymerizable monomer were sequentially added thereto, followed by stirring for about 1 hour. Subsequently, a black coloring agent (pigment dispersion) was added, and after adding other additives, the whole composition was finally stirred for 2 hours or more to prepare a photosensitive resin composition.

The specification of each component used for manufacture of the photosensitive resin composition is as follows.

(A) black colorant

(A-1) C.I. Millbase dispersion with blue pigment 15: 6 (solid content 15%) (SANYO company)

(A-2) C.I. Millbase dispersion with blue pigment 15: 3 (solid content 15%) (SANYO company)

(A-3) C.I. Millbase dispersion with violet pigment 29 (solid content 15%) (SAKATA Co., Ltd.)

(A-4) C.I. Millbase dispersion with red pigment 254 (solid 15%) (ENF Co., Ltd.)

(A-5) Millbase Dispersion with Organic Black Pigment (Solid 15%) (BASF Corporation)

(B) binder resin

Cardo Binder Resin (V259ME, Shinil Cheol Chemical Co., Ltd.)

(C) Photopolymerizable  Monomer

Dipentaerythritol hexa (meth) acrylate (DPHA, Japan Catalysts, Inc.)

(D) Photopolymerization Initiator

OXE01 (BASF Corporation)

(E) solvent

(E-1) Propylene Glycol Monomethyl Ether Acetate (PGMEA, Sigma-aldrich)

(E-2) ethylene glycol dimethyl ether (EDM, Sigma-aldrich)

(F) other additives

Leveling Agent (F-554, DIC Corporation)

(Unit: weight%) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 (A) black colorant (A-1) 0.753 1.506 2.259 3.012 - (A-2) 2.259 1.506 0.753 - - (A-3) 1.288 1.288 1.288 1.288 - (A-4) 3.365 3.365 3.365 3.365 - (A-5) - - - - 7.665 (B) binder resin 5.592 5.592 5.592 5.592 5.592 (C) photopolymerizable monomer 2.978 2.978 2.978 2.978 2.978 (D) photoinitiator 0.180 0.180 0.180 0.180 0.180 (E) solvent (E-1) 66.835 66.835 66.835 66.835 66.835 (E-2) 16.400 16.400 16.400 16.400 16.400 (F) other additives 0.350 0.350 0.350 0.350 0.350

Evaluation 1: Of Metal Ions Elution  Measure

(HPLC measurement)

After applying the photosensitive resin composition prepared in Examples 1 to 3, Comparative Example 1 and Comparative Example 2 to a thickness of 2.0㎛ on a substrate subjected to a predetermined pretreatment, and heated at 90 ℃ for 4 minutes to remove the solvent This formed the coating film. Subsequently, after exposing the photomask over the coating film at 40 mJ, the substrate on which the coating film was formed was baked at 220 ° C. for 25 minutes using a convection oven. The coating film specimens were then cut to a size of 1.5 cm * 3.0 cm and then immersed in a vial containing 10 g of NMP. The vial was held at 100 ° C. for 60 minutes, after which only NMP was collected. The collected NMP (eluate) was filtered using a 0.2 μm syringe filter, and then placed in a vial for HPLC to measure HPLC. The results are shown in Table 2 below. Measurement conditions are as follows.

-Column: Shiseido, Capcell pak, MGII, 4.6 mm × 250 mm, C18, 5 ㎛

Flow rate: 1 mL / min

-Injection Volume: 10 ㎕

-Column Oven Temperature: 40 ℃

Analysis time: 60 min

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 area (%) 12,000 15,000 29,000 38,000 52,000

From Table 2, in Examples 1 to 3 containing a phthalocyanine-based compound having a β-type crystal and a phthalocyanine-based compound having an ε-type crystal, the amount of organic elution is smaller than that of Comparative Example 1 and Comparative Example 2. You can check it. Furthermore, in Examples 1 and 2, the content of the phthalocyanine-based compound having β-type crystals was equal to or greater than that of the phthalocyanine-based compound having ε-type crystals. You can see that.

(UV-vis measurement)

After applying the photosensitive resin composition prepared in Examples 1 to 3 and Comparative Example 1 to a thickness of 2.0㎛ on a substrate subjected to a predetermined pretreatment, and then heated at 90 ℃ for 4 minutes to form a coating film It was. Subsequently, after exposing the photomask over the coating film at 40 mJ, the substrate on which the coating film was formed was baked at 220 ° C. for 25 minutes using a convection oven. Thereafter, 0.2 g of the coated film specimen was collected and immersed together with 10 g of the liquid crystal in a vial. After the vial was maintained at 100 ° C. for 60 minutes, only liquid crystals were collected, and the absorbance was measured using an analytical device (Agilent Cary 5000 UV-vis-NIR) on the collected liquid crystals. Indicated.

From FIG. 1, it can be seen that in Examples 1 to 3 including the phthalocyanine-based compound having β-type crystals and the phthalocyanine-based compound having ε-type crystals, the peak at 671 nm was reduced compared to Comparative Example 1. Furthermore, in Examples 1 and 2, in which the content of the phthalocyanine-based compound having β-type crystals was equal to or greater than that of the phthalocyanine-based compound having the ε-type crystals, the peak at 671 nm was significantly reduced than that of Comparative Example 1. You can check it. The peak at 671 nm is a peak for the elution of Cu-phthalocyanine blue, and it can be seen that the photosensitive resin composition according to the embodiment has high reliability by reducing the peak.

Evaluation 2: Measuring VHR Values

The photosensitive resin compositions prepared in Examples 1 to 3, Comparative Example 1 and Comparative Example 2 were applied onto a glass substrate patterned with ITO to form a coating film. The formed coating film and the patterned ITO electrode were assembled and pressed together, and then a liquid crystal was injected and sealed therebetween to fabricate a sample element. The VHR value of the sample device was measured using autronic VHRM (60 ° C., 10 Hz), and the results are shown in Table 3 below.

VHR value (%) Example 1 86.2 Example 2 76.4 Example 3 65.8 Comparative Example 1 60.1 Comparative Example 2 56.5

Through Table 3, in the case of Examples 1 to 3 using the phthalocyanine-based compound having β-type crystal and the phthalocyanine-based compound having ε-type crystal simultaneously as a blue pigment in the black colorant, Comparative Example 1 and Comparative Example 2 Compared with the case, it can be seen that the amount of metal ion elution is significantly reduced to prevent liquid crystal defects and to have excellent light shielding properties.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (15)

(A) a black colorant comprising a red pigment, a blue pigment and a violet pigment;
(B) binder resin;
(C) photopolymerizable monomer;
(D) photoinitiator; And
(E) solvent
Including,
The blue pigment includes a phthalocyanine compound having a β-type crystal and a phthalocyanine compound having an ε-type crystal,
The phthalocyanine-based compound having a β-type crystal is contained in an amount greater than or equal to the content of the phthalocyanine-based compound having an ε-type crystal.
Photosensitive resin composition.
delete The method of claim 1,
The phthalocyanine-based compound having the β-type crystals is contained in more content than the phthalocyanine-based compound having the ε-type crystals.
The method of claim 1,
The phthalocyanine-based compound having a β-type crystals include CI Pigment B15: 3, CI Pigment B15: 4, or a combination thereof.
The method of claim 1,
The phthalocyanine-based compound having an ε-type crystals include CI Pigment B15: 6.
The method of claim 1,
The red pigment may be pyrrolopyrrole-dione pigment, perylene pigment, anthraquinone pigment, dianthraquinone pigment, azo pigment, diazo pigment, quinacridone A photosensitive resin composition comprising a pigment, anthracene pigment or a combination thereof.
The method of claim 6,
The red pigment is a photosensitive resin composition represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
n1 and n2 are each independently an integer of 1-5.
The method of claim 1,
The violet pigment is a photosensitive resin composition represented by the following formula (2):
[Formula 2]

The method of claim 1,
The black colorant further comprises an orange pigment, yellow pigment or a combination thereof.
The method of claim 1,
The binder resin is a photosensitive resin composition comprising a cardo-based binder resin.
The method of claim 1,
The said photosensitive resin composition is with respect to the said total photosensitive resin composition total amount.
1% to 15% by weight of the black colorant (A);
1 wt% to 10 wt% of the (B) binder resin;
0.1 wt% to 10 wt% of the (C) photopolymerizable monomer;
0.1% to 5% by weight of the photopolymerization initiator (D); And
Residual amount of the solvent (E)
Photosensitive resin composition comprising a.
The method of claim 1,
The photosensitive resin composition further comprises an additive of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof.
The photosensitive resin film manufactured using the photosensitive resin composition of any one of Claims 1-12.
The method of claim 13,
The photosensitive resin film is a black column spacer.
The color filter containing the photosensitive resin film of Claim 13.

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