WO2015005546A1 - Black photosensitive resin composition and light blocking layer using same - Google Patents

Abstract

Provided are a black photosensitive resin composition and a light blocking layer using the same, the black photosensitive resin composition comprising: (A) a coloring agent containing lignin black; (B) an organic binder resin; (C) a photopolymerization monomer; (D) a photopolymerization initiator; and (E) a solvent.

Description

Black photosensitive resin composition and light shielding layer using same

The present substrate relates to a black photosensitive resin composition, a light shielding layer using the same, and a color filter.

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

The material used for such a light shielding layer is mainly carbon black. However, carbon black has been pointed out to be harmful to the human body, causing environmental pollution problems, it is urgent to develop alternatives.

Non-carbon materials that can be used as light-shielding materials include inorganic pigments such as titanium oxide and complex oxide pigments such as iron and manganese, black organic pigments, mixtures of inorganic pigments and black organic pigments, and the like. However, inorganic pigments have a problem of sedimentation due to their high specific gravity, and black organic pigments have a problem in that sufficient light shielding properties are not expressed.

Recently, the development trend of the light shielding layer material is directed toward lowering the film thickness of the light shielding layer by increasing the optical density (OD) as much as possible. This is because the film thickness of the light shielding layer is high, thereby minimizing the flatness damage that may occur. This is to ensure the drop margin of the liquid crystal even without.

One embodiment is to provide a black photosensitive resin composition having high optical density, excellent patternability and resolution.

Another embodiment is to provide a light shielding layer manufactured using the black photosensitive resin composition.

Another embodiment is to provide a color filter including the light blocking layer.

One embodiment includes (A) a colorant comprising lignin black; (B) organic binder resin; (C) photopolymerizable monomer; (D) photoinitiator; And (E) a black photosensitive resin composition comprising a solvent.

The colorant including the lignin black may further include a pigment, a dye, or a combination thereof.

The weight average molecular weight of the organic binder resin may be 1,000 g / mol to 100,000 g / mol.

The organic binder resin may be included in an amount of 10 parts by mass to 60 parts by mass based on 100 parts by mass of the solid content of the organic binder resin, the solid content of the photopolymerizable monomer, and the solid content of the photopolymerization initiator.

The black photosensitive resin composition may comprise (A) 1 wt% to 60 wt% of a colorant including the lignin black; (B) 0.5 wt% to 20 wt% of the organic binder resin; (C) 1% to 10% by weight of the photopolymerizable monomer; (D) 0.1% to 10% by weight of the photopolymerization initiator; And (E) may include the remaining amount of the solvent.

The photopolymerizable monomer is 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) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth Ta) acrylate, trimethylol propane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate, or a combination thereof.

The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; Radical polymerization initiators; Or an additive of a combination thereof.

The black photosensitive resin composition may be used for the light shielding layer.

Another embodiment provides a light shielding layer manufactured using the black photosensitive resin composition.

Another embodiment provides a color filter including the light blocking layer.

Specific details of other embodiments are included in the following detailed description.

Since a black photosensitive resin composition having high optical density, excellent patternability and resolution, and good dispersion stability is provided, it can be usefully applied to a light shielding layer used for a color filter or the like.

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 is a halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, imino group , Azido groups, amidino groups, hydrazino groups, hydrazono groups, carbonyl groups, carbamyl groups, thiol groups, ester groups, ether groups, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts 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, It means substituted with a substituent of C2 to C20 heterocycloalkyl group, C2 to C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C30 heteroaryl group or a combination thereof.

In addition, "hetero" means at least one hetero atom of at least one of N, O, S and P in the ring group unless otherwise specified in the present specification.

Also, unless stated otherwise in the present specification, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid". "Both mean it's possible.

Black photosensitive resin composition according to one embodiment includes (A) a colorant comprising lignin black; (B) organic binder resin; (C) photopolymerizable monomer; (D) photoinitiator; And (E) a solvent.

Since the lignin black has a high resistance characteristic, a separate coating process is unnecessary, harmless to the human body and environmentally friendly, and has an optical density, patternability, and resolution equivalent to that of a black photosensitive resin composition using a conventional black pigment. It can be used as a next-generation black photosensitive resin composition.

Each component is demonstrated concretely below.

(A) a colorant comprising lignin black

Lignin black is a black substance extracted from black solution, a balance of pulp made from wood, and is a natural polymer that can be easily decomposed by microorganisms in the ground.

Carbon black, which is mainly used as a light blocking layer material, is harmful to the human body and causes environmental pollution problems, whereas the lignin black is an environmentally friendly material and harmless to the human body, and high optical density can be obtained without inhibiting resolution and the like.

A colorant including the lignin black may be used in the black photosensitive resin composition in the form of a dispersion by preparing a lignin black dispersion by mixing the colorant, a dispersant, a solvent, and the like. Specifically, a mixture of the lignin black, a dispersant, a solvent, and the like mixed at the same time may be dispersed for a predetermined time to prepare a lignin black dispersion, which may be used in the black photosensitive resin composition.

The dispersant may help to uniformly disperse the colorant including the lignin black in the solvent.

Examples of the dispersant include nonionic compounds, anionic compounds, cationic compounds, or combinations thereof, and specific examples thereof include polymer dispersants such as polyethyleneimine dispersants, urethane dispersants, and acrylic dispersants.

Examples of commercially available products of the dispersant include, for example, DISKBY-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, 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; Solvese S3000, S9000, S17000, S20000, S27000, S24000, S26000, S28000 from Avecia; Or PB711, PB821 from Ajinomoto.

The dispersant may be included in about 0.1 to 15% by weight based on the total amount of the black photosensitive resin composition. When the dispersant is included in the above range, the dispersibility of the black photosensitive resin composition is excellent in the stability, developability and patternability in manufacturing the light shielding layer.

The solvent is as described later.

The colorant including the lignin black may further include a pigment, a dye, or a combination thereof in order to control light blocking properties and color characteristics of the lignin black.

The pigment may be used in organic pigments, inorganic pigments or a combination thereof. Among them, the organic pigment and the inorganic pigment may be mixed and used for high optical density.

The organic pigment may be used a black organic pigment. The black organic pigment is insulative.

Examples of the black organic pigments include perylene black and cyanine black, and these may be used alone or in combination of two or more thereof.

The black organic pigments may also be used by mixing two or more organic pigments to have a black color. Any pigment can be used as long as it is a combination of pigments that are black when mixed on the color coordinates, for example, red pigments, blue pigments, green pigments, purple pigments, yellow pigments, cyanine pigments, and magenta. It can be used by blackening by selecting from two types of pigments, combining two or more types. For example, red pigments, blue pigments and green pigments may be mixed and blackened, or green pigments and purple pigments may be mixed and blackened.

Examples of the red pigment include perylene pigments, anthraquinone pigments, dianthraquinone pigments, azo pigments, diazo pigments, quinacridone pigments, anthracene pigments, and the like. have. Specific examples of the red pigment include perylene pigments, quinacridone pigments, naphthol AS, cuminamine pigments, anthraquinones (sudan I, II, III, R), dianthraquinoneyllets, Vis azo, benzopyrrole, etc. are mentioned.

Examples of the blue pigment include metal phthalocyanine pigments, indanthrone pigments, and indophenol pigments. Specific examples of the blue pigment include phthalocyanine metal complexes such as copper phthalocyanine, chloro copper phthalocyanine, chloro aluminum phthalocyanine, titanyl phthalocyanine, vanazin phthalocyanine, magnesium phthalocyanine, zinc phthalocyanine, cobalt phthalocyanine, and the like.

Examples of the green pigment include halogenated phthalocyanine pigments. Specifically, polychloro copper phthalocyanine, polychloro bromine phthalocyanine, etc. are mentioned.

Examples of the violet pigment include dioxazine violet, first violet B, methyl violet lake, indanthrene brilliant violet, and the like.

Examples of the yellow pigment include a tetra chloro isoindolinone pigment, a hansa pigment, a benzidine yellow pigment, and an azo pigment. Specifically, hansa yellow (10G, 5G, 3G, G, GR, A, RN, R), benzidine (G, GR), chrome yellow, permanent yellow ) (FGL, H10G, HR) and the like.

Examples of the cyanine pigments include metal-free phthalocyanine and merocyanine.

The magenta pigment may be dimethyl quinacridone, thio indigo, or the like.

Examples of the inorganic pigment include carbon black, chromium oxide, iron oxide, titanium black, titanium carbon, and the like. Such inorganic pigments exhibit resistance characteristics and may be used alone or in combination of two or more.

The organic pigments and inorganic pigments may be mixed and used in a weight ratio of about 1 to 10: 1, for example, may be used in a weight ratio of about 2 to 7: 1. When mixed and used within the weight ratio range, the processability can be stabilized and a low dielectric constant can be ensured.

The dispersant may be used together to disperse the pigment well in the black photosensitive resin composition.

The dispersant may be added to the inside of the pigment in the form of surface treatment of the pigment in advance, or may be used in the production of a black photosensitive resin composition with the pigment.

Pigments, dyes, or combinations thereof that may be further included in the colorant including the lignin black may be included in about 1% by weight to 40% by weight based on the total solids of the black photosensitive resin composition, for example, about 5% by weight % To 30% by weight may be included. When the colorant is included in the above range, excellent insulation, high optical density can be obtained, and excellent processability such as developability can be ensured.

The colorant including the lignin black may be included in an amount of about 10 wt% to 70 wt%, for example, about 40 wt% to 60 wt%, based on the total solids of the black photosensitive resin composition. When using the colorant containing the lignin black in the above range, it is easy to disperse in the solvent, it is possible to obtain a high optical density without inhibiting the resolution and the like.

(B) organic binder resin

As the organic binder resin, cardo binder resin, acrylic binder resin, polyimide binder resin, polyurethane binder resin, or a combination thereof can be used. The binder resin may be a cardo resin, or a mixture of a cardo resin and an acrylic resin. When using the cardo-based resin or a mixture of the cardo-based resin and the acrylic resin, heat resistance, chemical resistance and adhesion of the photosensitive resin composition may be improved.

The weight average molecular weight of the organic binder resin may be about 1,000 g / mol to 100,000 g / mol. If the weight average molecular weight of the said organic binder resin is about 1,000 g / mol or more, a coating film can be made uniform, and developability becomes favorable that the weight average molecular weight of the said organic binder resin is about 100,000 g / mol or less.

Among the organic binder resins, cardo-based binder resins may be preferably used. When the cardo-based binder resin is used, heat resistance and chemical resistance of the black photosensitive resin composition may be improved.

The cardo-based binder resin may be a compound including a repeating unit represented by Formula 1 below.

[Formula 1]

(In Formula 1,

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, a hydrogen atom or CH ₂ OR _a (R _a is a vinyl group, an acryl group or a methacryl group),

R ₃₀ is the same as or different from each other, a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, an acryl group, or a methacryl group,

Z ₁ is the same or different from each other, a single bond, O, CO, SO ₂ , CR _b R _c , SiR _d R _e (where R _b to R _e are the same or different from each other, a hydrogen atom, or a substituted or unsubstituted Ring is a C1 to C20 alkyl group), or any one of compounds represented by the following formula (2) to 12,

Z ₂ is the same as or different from each other, and is an acid anhydride residue or an acid dianhydride residue.)

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

(In Chemical Formula 6,

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 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

Specifically, the cardo-based binder resin may be obtained by reacting a compound represented by the following Chemical Formula 13 with tetracarboxylic dianhydride.

[Formula 13]

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 weight average molecular weight of the cardo-based binder resin may be about 1,000 g / mol to 20,000 g / mol, specifically about 3,000 g / mol to 10,000 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 manufacturing the light shielding film.

The acrylic resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin including one or more acrylic repeating units.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof may include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5 wt% to 50 wt%, for example, 10 wt% to 40 wt%, based on the total amount of the acrylic resin.

The second ethylenically unsaturated monomer is an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethyl ether, etc .; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds, such as vinyl acetate and a vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; Vinyl cyanide compounds such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These etc. can be mentioned, These can be used individually or in mixture of 2 or more.

Specific examples of the acrylic resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer And methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc. are mentioned, It is not limited to these, These can also be used individually or in combination of 2 or more types.

The weight average molecular weight of the acrylic resin may be from 3,000 g / mol to 150,000 g / mol, for example 5,000 g / mol to 50,000 g / mol, for example 2,000 g / mol to 30,000 g / mol can be. When the weight average molecular weight of the acrylic resin is within the above range, the physical and chemical properties of the photosensitive resin composition are excellent, the viscosity is appropriate, and the adhesion to the substrate in the manufacture of light shielding layer, column spacer or black spacer is excellent.

The acid value of the acrylic resin may be 15 mgKOH / g to 150 mgKOH / g, for example 80 mgKOH / g to 130 mgKOH / g. When the acid value of the acrylic resin is within the above range, the resolution of the pixel pattern is excellent.

Specifically, the organic binder resin is a monomer having a carboxyl group such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl meta Acrylate, 2-hydroxypropyl methacrylate, N-butyl acrylate, N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, Phenoxy methacrylate, isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, copolymers with styrene, acrylamide, acrylonitrile and the like, and phenol novolak type epoxy acrylate polymers, phenol Novolac-type epoxy methacrylate polymer, Cresol novolac-type epoxy acrylate polymer, Cresol novolac-type E When there may be mentioned a methacrylate polymer, a bisphenol A type epoxy acrylate polymer, a bisphenol S type epoxy acrylate polymers, anhydride adducts of Kadoma epoxy acrylate.

Content of the monomer component which has carboxyl groups, such as acrylic acid and methacrylic acid, which comprise the said organic binder resin is about 5 mol%-50 mol%, for example, about 10 mol%-40 mol% based on 100 mol% of organic binder resins. Can be.

The weight average molecular weight of the organic binder resin may be about 1,000 g / mol to 100,000 g / mol. If the weight average molecular weight of the said organic binder resin is about 1,000 g / mol or more, a coating film can be made uniform, and developability becomes favorable that the weight average molecular weight of the said organic binder resin is about 100,000 g / mol or less.

The organic binder resin may be included in an amount of about 10 parts by weight to 60 parts by weight based on 100 parts by weight of the total content of the solid content of the organic binder resin, the solid content of the photopolymerizable monomer, and the photopolymerization initiator. Since the organic binder resin is included in about 10 parts by weight or more based on 100 parts by weight of the total content of the solid content of the organic binder resin, the solid content of the photopolymerizable monomer, and the photopolymerization initiator, the film can be easily formed during application and drying. After curing, the film strength can be sufficiently increased. In addition, the organic binder resin may be included in an amount of about 60 parts by weight or less based on 100 parts by weight of the total content of the solid content of the organic binder resin, the solid content of the photopolymerizable monomer, and the photopolymerization initiator, thereby improving developability.

The organic binder resin may be included in about 0.5% to 20% by weight of the total amount of solids of the black photosensitive resin composition, specifically, may be included in about 1% to 10% by weight. When the organic binder resin is included in the above range, the viscosity is appropriately maintained to excellent in patternability, processability and developability in manufacturing a light shielding film.

(C) photopolymerizable monomer

The photopolymerizable monomer is a monomer or oligomer generally used in a black photosensitive resin composition, and a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond may be used.

Specific examples of the photopolymerizable monomer include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol Diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, bisphenol A epoxy acrylate , Ethylene glycol monomethyl ether acrylate, trimethylolpropane triacrylate, trisacryloyloxyethyl phosphate, cardoepoxy diacrylate, and the like.

Examples of commercially available products of the reactive unsaturated compounds 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 .; And V-158 ^® and V-2311 ^{® from} Osaka Yuki Chemical Co., Ltd. The (meth) transfer function of an example esters of acrylic acid is such as doah Gosei Kagaku Kogyo Co., Ltd.'s Aronix M-210 ^®, the same M-240 ^®, the same M-6200 ^®; Nihon Kayaku Co., Ltd. KAYARAD HDDA ^® , HX-220 ^® , R-604 ^®, etc .; And V-260 ^® , V-312 ^® and V-335 HP ^{® from} Osaka Yuki Chemical Co., Ltd. The (meth) three examples of the polyfunctional ester of acrylic acid, doah Gosei Kagaku Kogyo Co., Ltd.'s Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, copper 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 Kogyo Co., Inc. V-295 ^®, East -300 ^®, East -360 ^®, East -GPT ^®, East -3PA ^®, and the like Dong -400 ^®. The above products can be used alone or in combination of two or more.

The photopolymerizable monomer may be included in an amount of about 1 wt% to 20 wt%, and specifically, about 1 wt% to 15 wt% based on the total solids of the black photosensitive resin composition. When the photopolymerizable monomer is included in the above range, compatibility with the organic binder resin is improved, so that the light shielding film has excellent sensitivity in the presence of patterning and oxygen and a smooth surface film can be obtained.

(D) photoinitiator

The photopolymerization initiator is a photopolymerization initiator generally used in the black photosensitive resin composition, for example, an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, or the like can be used. Can be.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloro acetophenone, pt-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc. are mentioned.

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

Examples of the thioxanthone compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone etc. are mentioned.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal and the like.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) -s-triazine and 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 (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-methoxynaphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,3,4 Bis (trichloromethyl) -6-piperonyl-s-triazine, 2,3,4-bis (trichloromethyl) -6- (4-methoxystyryl) -s-triazine and the like Can be.

Examples of the oxime compound include O-acyl oxime compound, 2- (O-benzoyl oxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 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 and 1- (4-phenylsulfanylphenyl) -butan-1-one oxime- O-acetate or the like can be used.

In addition to the above compound, the photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, a biimidazole compound, or the like.

The said photoinitiator can be used individually or in combination of 2 or more types.

The photopolymerization initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light and transferring energy after being excited.

The photopolymerization initiator may be included in an amount of about 1 part by mass to 40 parts by mass based on 100 parts by mass of the total content of the photopolymerizable monomer and the photopolymerization initiator.

The photopolymerization initiator may be included in about 0.1 wt% to 10 wt% with respect to the total solids of the black photosensitive resin composition, and specifically, may be included in about 1 wt% to 5 wt%. When the photopolymerization initiator is included in the above range, the sensitivity of the radical is good, the color concentration of the black photosensitive resin composition solution is properly maintained, and the decrease in transmittance due to the unreacted initiator can be prevented.

(E) solvent

The solvent may be a material having compatibility with the colorant including the lignin black, the organic binder resin, the photopolymerizable monomer, and the photopolymerization initiator, but not reacting.

Examples of the solvent 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, acetyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, Ethyl benzoate, 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 the balance of the total amount of solids of the black photosensitive resin composition, specifically, may be included in about 50% by weight to 70% by weight. When the solvent is included in the above range, as the black photosensitive resin composition has an appropriate viscosity, processability in manufacturing a light shielding layer is excellent.

(F) other additives

The photosensitive resin composition includes malonic acid to prevent spots and spots upon application, to improve leveling performance, and to prevent generation of residue by undeveloped; 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 ^® , and the like by BM Chemie; Mecha Pack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^®, etc. by Dai Nippon Inky Chemical Co., Ltd .; Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^®, etc. of Sumitomo 3M Corporation; Asahi Grass Co., Ltd. Saffron S-112 ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^®, etc .; Toray Silicone Co., Ltd.'s SH-28PA ^{®, ®} -190 copper, may be a commercially available product such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The content of the additive can be easily adjusted according to the desired physical properties.

The photosensitive resin composition may further include an epoxy compound in order to improve adhesion to a substrate.

As an example of the said epoxy compound, a phenol novolak epoxy compound, a tetramethyl biphenyl epoxy compound, a bisphenol-A epoxy compound, an alicyclic epoxy compound, or a combination thereof is mentioned.

The epoxy compound may be included in an amount of about 0.01 parts by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition for color filters, and specifically, about 0.1 parts by weight to 5 parts by weight. When the epoxy compound is included in the above range, it is excellent in adhesion, heat resistance and chemical resistance.

Another embodiment provides a light blocking layer manufactured using the black photosensitive resin composition described above.

The manufacturing method of the said light shielding layer is as follows.

(1) Coating and coating film forming step

After applying the above-mentioned photosensitive resin composition to a desired thickness, such as 0.5 μm or 25 μm, by spin or slit coating, roll coating, screen printing, applicator, etc. The coating is formed by heating the solvent for about 1 to 10 minutes at a temperature of from < RTI ID = 0.0 >

(2) exposure step

In order to form a pattern required for the coating film obtained as described above, an active line of 190 nm to 500 nm is irradiated after interposing a mask of a predetermined form. Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, argon gas lasers, and the like can be used as light sources used for irradiation.

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

(3) Development stage

Following the exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary portions, leaving only the exposed portion to form an image pattern.

(4) post-processing step

Since an image pattern obtained by the above development can be obtained in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, storage stability, and the like, it can be cured by performing additional heating or active ray irradiation. .

By using the black photosensitive resin composition mentioned above, the outstanding adhesiveness and optical density calculated | required by the light shielding layer can be obtained.

Another embodiment provides a color filter including the light blocking layer. The light shielding layer described above may be used for a color filter or 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.

(Preparation of lignin black dispersion)

Premix by mixing 100 g of lignin black and 30 g of dispersant (BYK165) with 370 g of solvent (PGMEA), and using a bead-type disperser NanoGran Mill (manufactured by Asada Iron Works) using 0.2 mm beads until the dispersed particle system reaches 100 nm. Dispersion over time gave a lignin black dispersion.

Example 1: Preparation of black photosensitive resin composition

After dissolving a photoinitiator in a solvent, it fully stirs at room temperature for about 30 minutes. The organic binder resin and the photopolymerizable monomer are added thereto and stirred for 1 hour. Then, 60 g (54 wt%) of lignin black dispersion was added and stirred for about 2 hours to filter the solution three times to remove impurities, thereby preparing a black photosensitive resin composition.

Example 2: Preparation of black photosensitive resin composition

A black photosensitive resin composition was prepared in the same manner as in Example 1, except that 50 g (50 wt%) of lignin black dispersion and 34.6 g of a solvent were used.

Comparative Example 1: Preparation of black photosensitive resin composition

A black photosensitive resin composition was manufactured in the same manner as in Example 1, except that 55 g (52 wt%) of carbon black dispersion No. 3877 (manufactured by Tokushiki) and 34.56 g of a solvent were used instead of the lignin black dispersion.

Comparative Example 2: Preparation of Black Photosensitive Resin Composition

A black photosensitive resin composition was manufactured in the same manner as in Example 1, except that 100 g (60 wt%) of titanium black dispersion No. 1043 (manufactured by MIKUNI) and 9.38 g of a solvent were used instead of the lignin black dispersion.

Each component and content used in the preparation of the black photosensitive resin composition according to Example 1, Example 2, Comparative Example 1 and Comparative Example 2 are shown in Table 1 below.

Table 1

	Example 1	Example 2	Comparative Example 1	Comparative Example 2
Lignin Black Dispersion	60 g	50 g	-	-
Carbon Black Dispersion No.3877 (TOKUSHIKI)	-	-	55 g	-
Titanium Black Dispersion No.1043 (MIKUNI)	-	-	-	100 g
Photopolymerization initiator OXE02 (BASF)	1.5 g	1.5 g	1.5 g	1.5 g
Photopolymerizable monomer (dipentaerythritol hexa acrylate, DPHA)	3 g	3 g	3 g	3 g
Organic Binder Resin (Cado Epoxy Acrylate, V259 (Shin-Nitetsu Chemical Co., Ltd.))	10 g (5.5 g of solids)	10 g (5.5 g of solids)	10 g (5.5 g of solids)	10 g (5.5 g of solids)
Solvent (propylene glycol monomethyl ether acetate, PGMEA)	34.5 g	34.6 g	34.56 g	9.38 g
Silane Coupling Agent # 554 (DIC)	1000 ppm	1000 ppm	1000 ppm	1000 ppm

Evaluation 1: Optical Density Measurement

The black photosensitive resin composition of Example 1, Example 2, Comparative Example 1, and Comparative Example 2 was apply | coated with a spin coater, respectively, on the glass substrate of thickness 0.7mm which wash | cleaned cleanly, and it was carried out on the hot plate of 90 degreeC Drying for minutes gave each coating film about 1.0 탆 thick. The optical density of each coating film was measured using 310TR optical density meter (Exlite). The results are shown in Table 2 below.

<Evaluation Criteria>

○: optical density is more than 3.7

△: optical density is 2.5 GHz or more and less than 3.7

X: optical density less than 2.5

Evaluation 2: Resolution Measurement

Each of the coating films according to Examples 1 to 3, Comparative Example 1 and Comparative Example 2 obtained in the above Evaluation 1 was used as a broadband exposure machine having a peak of 365 nm in wavelength using a pattern mask having a line width of 2 µm to 10 µm. mJ / cm ² irradiation. (USHIO's Proximity Exposure System was equipped with a UV filter that blocks wavelengths below 350nm so that light below 350nm is not irradiated.) After stabilizing at 23 ° C with 0.04% aqueous potassium hydroxide solution, 1.0 kg / cm ² Spray development was performed for 60 seconds at the spray pressure. The pattern obtained by this method was cured by heating in an oven at 220 ° C. for 30 minutes, and then the minimum pattern was observed using an optical microscope. The results are shown in Table 2 below. Resolution values shown in Table 2 below are the minimum reproduced line widths.

TABLE 2

	Optical density	Resolution (μm)
Example 1	○	5
Example 2	○	4
Comparative Example 1	○	4.5
Comparative Example 2	△	6

Through the Table 2, the black photosensitive resin composition of Examples 1 and 2 including a colorant, an organic binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent containing lignin black according to one embodiment, the existing carbon dispersion The optical density and resolution similar to those of the black photosensitive resin composition of Comparative Example 1, which were used, showed superior optical density and resolution than the black photosensitive resin composition of Comparative Example 2, which used the conventional titanium black dispersion, thereby being environmentally friendly and excellent optical properties. It can be seen that it can be usefully used as a black photosensitive resin composition.

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 (10)

1. (A) a colorant comprising lignin black;

   (B) organic binder resin;

   (C) photopolymerizable monomer;

   (D) photoinitiator; And

   (E) solvent

   Black photosensitive resin composition comprising a.
2. The method of claim 1,

   The black photosensitive resin composition comprising a colorant comprising the lignin black further comprises a pigment, a dye, or a combination thereof.
3. The method of claim 1,

   The black photosensitive resin composition having a weight average molecular weight of the organic binder resin is 1,000 g / mol to 100,000 g / mol.
4. The method of claim 1,

   The organic binder resin is a black photosensitive resin composition containing 10 parts by mass to 60 parts by mass with respect to 100 parts by mass of the solid content of the organic binder resin, the solid content of the photopolymerizable monomer, and the total solid content of the photopolymerization initiator.
5. The method of claim 1,

   The black photosensitive resin composition is based on the total amount of solids of the black photosensitive resin composition.

   (A) 1% to 60% by weight of a colorant comprising the lignin black;

   (B) 0.5 wt% to 20 wt% of the organic binder resin;

   (C) 1% to 10% by weight of the photopolymerizable monomer;

   (D) 0.1% to 10% by weight of the photopolymerization initiator; And

   (E) the solvent residual amount

   Black photosensitive resin composition comprising a.
6. The method of claim 1,

   The photopolymerizable monomer is 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) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth A black photosensitive resin composition containing a) acrylate, trimethylol propane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate, or a combination thereof.
7. The method of claim 1,

   The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; Radical polymerization initiators; Or black photosensitive resin composition containing the additive of these combinations further.
8. The method of claim 1,

   The said black photosensitive resin composition is a black photosensitive resin composition used for a light shielding layer.
9. The light shielding layer manufactured using the black photosensitive resin composition of any one of Claims 1-8.
10. A color filter comprising the light blocking layer of claim 9.