TWI521304B - Black photosensitive resin composition and light blocking layer using the same - Google Patents

Description

Black photosensitive resin composition and light shielding layer using the same Cross-references for related applications

The present application claims the priority and benefit of the Korean Patent Application No. 10-2013-0081723, filed on Jan. 11, 2013, the disclosure of which is hereby incorporated by reference.

(a) Field of invention

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

(b) Related technical description

A black photosensitive resin composition is used to manufacture a display device for a color filter, a liquid crystal display material, an organic light emitting element (EL), a display flat material, and the like. For example, a color filter such as a color liquid crystal display requires a light shielding layer on the boundary between color layers such as red, green, and blue to enhance the display pair or chromophore effect. This light shielding layer can be mainly formed of a black photosensitive resin composition. The light shielding layer is mainly formed by using a carbon black. However, carbon black has the problem of being harmful to the human body and causing environmental pollution, and it is extremely urgent to develop alternatives. On the other hand, the non-carbon material which can be used as the light shielding material may contain an inorganic coloring material such as titanium sillimanite Black (titan black), iron/manganese composite oxide coloring material, etc.; black organic coloring material; inorganic coloring material and black organic coloring material mixture. However, the inorganic colorant settles due to the heavy specific gravity, and the black organic colorant cannot achieve sufficient light shielding characteristics. Recently, the development of the light shielding layer material has focused on reducing the thickness of the light shielding layer by increasing the optical density (OD) to the maximum, so that the flatness damage due to the high thickness of the light shielding layer can be minimized, and the dripping method is ensured. The limit of adding liquid crystal can be ensured without an overcoat.

Summary of invention

One embodiment provides a black photosensitive resin composition having high optical density and excellent patterning properties and resolution.

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

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

An embodiment provides a black photosensitive resin composition comprising (A) a lignin-containing coloring agent; (B) an organic binder resin; (C) a photopolymerizable monomer; (D) a light a polymerization initiator; and (E) a solvent.

The lignin-containing coloring agent may further comprise a colorant, a dye, or a combination thereof.

The organic binder resin may have a weight average molecular weight of from 1,000 g/m to 100,000 g/mole.

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

The black photosensitive resin composition may comprise (A) 1% by weight to 60% by weight of a lignin-containing coloring agent; (B) 0.5% by weight to 20% by weight of an organic binder resin; (C) 1% by weight to 10% by weight of light a polymerizable monomer; (D) 0.1% by weight to 10% by weight of a photopolymerization initiator; and (E) a balance of a solvent.

The photopolymerizable monomer may 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(methyl) ) acrylate, pentaerythritol di(meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, Dipentaerythritol tri(meth)acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (A) Acrylate, trimethylolpropane tri(meth)acrylate, tris(meth)acryloxyethyl phosphate, novolac epoxy (meth) acrylate, or a combination thereof.

The photosensitive resin composition may further comprise malonic acid; 3-amino-1,2-propanediol; a decane-based coupling agent having a vinyl group or a (meth)acryloxy group; a leveling agent; a fluorine-based surfactant; a radical polymerization initiator; or a combination of these additives.

The black photosensitive resin composition can be used for a light shielding layer.

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

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

Other embodiments are included in the detailed description below.

A black photosensitive resin composition having high optical density, excellent patterning properties, and resolution is provided, and can be usefully applied to form a light shielding layer or the like for a color filter or the like.

Detailed description

Hereinafter, embodiments of the invention are described in detail. However, such embodiments are illustrative, and the disclosure is not limited thereto.

As used herein, when a particular definition is not otherwise provided, the term "substituted" refers to a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group. a mononitro group, a cyano group, an amine group, an imine group, a monoazide group, a monomethyl group, a fluorenyl group, an anthranylene group, a carbonyl group, a monomethylmercapto group, a monothiol group, a monoester group, a monoether group, a monocarboxy group or a salt thereof, a monosulfonic acid group or a salt thereof, a monophosphoric acid or the same a salt, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C3 to C20 cycloalkyl group, a C3 To a C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group a C3 to C30 heteroaryl group, or a combination of such substituents, replacing at least one of the hydrogens Daiji.

As used herein, when a particular definition is not otherwise provided, the term "hetero" may refer to replacing at least one C of a cyclic group with at least one heteroatom of N, O, S, and P.

As used herein, when a particular definition is not otherwise provided, "(meth)acrylate" means "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic" And "methacrylic acid".

According to one embodiment, the black photosensitive resin composition comprises (A) a lignin-containing coloring agent; (B) an organic binder resin; (C) a photopolymerizable monomer; (D) a photopolymerization Starting agent; and (E) a solvent.

Since lignin black has a high resistance characteristic, the black photosensitive resin composition according to an embodiment does not require an individual coating method, does not cause harm to humans, and is environmentally friendly, but still has a conventional black color with a black color material. Since the photosensitive resin composition has the same optical density, patterning property, and resolution, it can be used as a next-generation black photosensitive resin composition.

Hereinafter, each component is specifically exemplified.

(A) a coloring agent containing lignin black

The lignin black is a black material extracted from a black solution, which is a residual solution for making pulp obtained from wood, and is also a natural polymer material which is easily decomposed by microorganisms under the ground.

When used mainly as a light-shielding layer material, lignin black is environmentally friendly and harmless to the human body. Furthermore, high optical density is achieved without deteriorating the resolution, and carbon black is indeed harmful to the human body, causing environmental pollution problems.

Since a lignin-containing coloring agent is mixed with a dispersing agent, a solvent, or the like to prepare a lignin black dispersion, a dispersion of lignin black can be used for the black photosensitive resin composition. Specifically, the lignin black is mixed with a dispersing agent, a solvent or the like at the same time, and one of the lignin blacks can be obtained for the black photosensitive resin composition by dispersing the mixture for a predetermined time.

The dispersing agent can help the lignin-containing coloring agent to be uniformly dispersed in the solvent.

Examples of the dispersing agent may be a nonionic compound, an anionic compound, a cationic compound, or a combination thereof, and a specific example may be a polymeric dispersant, such as a polyethylenimine. The dispersant, a dispersant mainly composed of urethane, a dispersant mainly composed of acrylic acid, and the like.

Commercially available examples of the dispersant may include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164 manufactured by BYK Co., Ltd. DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49 manufactured by EFKA Chemicals Co. , EFKA-100, EFKA-400, EFKA-450, etc.; Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000 manufactured by Zeneka Co.; Avecia Inc. Manufactured Solsperse S3000, S9000, S17000, S20000, S27000, S24000, S26000, S28000, etc.; or PB711, PB821, etc. manufactured by Ajinomoto Inc.

The dispersant may be contained in an amount of about 0.1 to 15% by weight based on the total weight of the black photosensitive resin composition. When the dispersing agent is contained in this range, the black photosensitive resin composition can have excellent dispersing properties, and therefore, stability, developability, and patterning properties are obtained when forming a light shielding layer.

The solvent system is the same as described later.

The lignin-containing coloring agent may further comprise a colorant, a dye, or a combination thereof to adjust the light-shielding properties and color characteristics of the lignin black.

The colorant may comprise an organic colorant, an inorganic colorant, or a combination thereof. Organic and inorganic pigments can be mixed to achieve high optical density.

The organic colorant can be a black organic colorant.

Black organic pigments can have an insulating property.

The black organic coloring material may include flower black, cyanine black, etc., and these coloring materials may be used singly or in combination of two or more.

The black organic colorant may be one of the black colorants obtained by mixing more than two organic colorants. The black organic colorant may be included in any color material combination in which the color coordinates show black, and for example, by combining a color material selected from a red color, a color material mainly based on blue, and a green color. The color material, a purple-based coloring material, a yellow-based coloring material, a cyan-based coloring material, and a magenta-based coloring material of two or more And, obtained by blackening this combination. For example, a red-based coloring material, a blue-based coloring material, and a green-based coloring material are mixed and blackened, or a green-based coloring material and a purple-based coloring material. The colorants are mixed and blackened.

The red-based coloring material may include a coloring material mainly composed of bismuth, a coloring material mainly composed of bismuth, a coloring material mainly composed of bismuth, and an azo-based coloring material. A coloring material mainly composed of diazo, a coloring material mainly composed of quinacridone, and a coloring material mainly composed of cerium. A specific example of a red-based coloring material may include a coloring material, a quinophthalone coloring material, a naphthol AS, a sicomin coloring material, and a sputum (Sudan I, II, III, R). ), ditelluride, disazo, benzopyrene, and the like.

The blue-based coloring material may include a coloring material mainly composed of metal phthalocyanine, a coloring material mainly composed of indanthrone, and a coloring material mainly based on indophenol. Other examples of blue-based colorants may include a phthalocyanine metal complex such as beryl cyanine, chloroaluminum phthalocyanine, chloroaluminum phthalocyanine, oxytitanium phthalocyanine, vanadic acid. Indigo cyanine, magenta cyanine, zinc phthalocyanine, sorghum cyanine, cobalt cyanine and so on.

The green-based coloring material may include a coloring material mainly composed of halogenated phthalocyanine. In particular, the green-based coloring material may include polychlorinated copper phthalocyanine, polychlorobromophthalocyanine, and the like.

The color based on purple can contain two Purple, first purple B, methyl violet, indanthrene bright purple and so on.

The pigment mainly composed of yellow may contain a coloring matter mainly composed of tetrachloroisoindolinone, a coloring material mainly composed of hansa, and a yellow benzidine yellow. The main color material, a azo-based color material. In particular, yellow-based pigments may include Hansa Yellow (10G, 5G, 3G, G, GR, A, RN, R), benzidine (G, GR), chrome yellow, permanent yellow (FGL, H10G). , HR), 蒽, etc.

The coloring material mainly composed of cyanine may include non-metal phthalocyanine, merocyanine, and the like.

The coloring agent based on magenta may comprise dimethylquinacridone or thioindigo.

The inorganic colorant may include carbon black, chromium oxide, iron oxide, titanium sillimanite black, titanium carbide, aniline black, and the like. This inorganic colorant may have electrical resistance characteristics and may be used singly or in combination of two or more.

The organic colorant and the inorganic colorant may be mixed in a weight ratio of from about 1 to about 10:1 and, for example, in a weight ratio of from about 2 to about 7:1. When the organic colorant and the inorganic colorant are mixed in this weight ratio range, stable processability and low dielectric constant are ensured.

The dispersant can be used to disperse the colorant well in the black photosensitive resin composition.

In particular, the colorant may be pretreated with a dispersant surface, or the colorant and dispersant may be added together during the preparation of the black photosensitive resin composition.

The colorant, the dye, or the like, which is contained in the lignin-containing coloring agent, may be 1 wt% to 40 wt% and, for example, about 5 wt% to 30 wt%, based on the total amount of the black photosensitive resin composition. The amount is included. When the colorant is contained in this range, excellent processability such as developability and the like, excellent insulating properties, and high optical density can be obtained.

The lignin-containing coloring agent may be included in an amount of from about 10% by weight to 70% by weight and, for example, from about 40% by weight to 60% by weight based on the total solid content of the black photosensitive resin. When the coloring agent containing lignin black is used in this range, the coloring agent can be easily dispersed in a solvent, and high optical density can be obtained without deterioration of resolution or the like.

(B) Organic binder resin

The organic binder resin may comprise a cardo-based binder resin, an acrylic-based binder resin, a polyimine-based binder resin, and a polyurethane-based bond. Resin, or a combination of these. The binder resin may comprise a bismuth-based resin or a mixture of a bismuth-based resin and an acrylic-based resin. Heat resistance, chemical resistance, and close contact properties of a photosensitive resin composition when a resin based on ruthenium or a mixture of a ruthenium-based resin and an acrylic-based resin is used. Can be improved.

The organic binder resin may have a weight average molecular weight of from about 1,000 g/m to 100,000 g/mole. When the organic binder resin has a weight average molecular weight of greater than or equal to about 1,000 grams per mole, one layer may be uniformly formed, and the organic binder resin has a weight average molecular weight of less than or equal to about 100,000 grams per mole. Satisfactory developability.

The organic binder resin is preferably a binder resin mainly composed of ruthenium. The binder resin based on ruthenium improves the heat resistance and chemical resistance of the black photosensitive resin composition.

The ruthenium-based binder resin may be a compound containing a repeating unit represented by the following Chemical Formula 1.

In the above Chemical Formula 1, R ₂₄ to R ₂₇ are the same or different and are one hydrogen atom, one halogen element, or a substituted or unsubstituted C1 to C20 alkyl group, and R ₂₈ and R ₂₉ are the same. Or different, and is a hydrogen atom or CH ₂ OR _a (R _a monovinyl group, a propenyl group, or a monomethacryl group), R ₃₀ is the same or different, and is a hydrogen atom a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a propenyl group, or a monomethacryl group, the Z ₁ system is the same Or different, and is a single bond, O, CO, SO ₂ , CR _b R _c , SiR _d R _e (wherein R _b to R _e are the same or different and are one hydrogen atom, or substituted or unsubstituted The C1 to C20 alkyl group), or one selected from the group consisting of the compounds represented by the following Chemical Formulas 2 to 12, and the Z ₂ is the same or different, and is an acid anhydride residual group or a monobasic acid anhydride residue.

In the above 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.

The binder resin mainly based on ruthenium can be obtained by reacting a compound represented by the following Chemical Formula 13 with a tetracarboxylic dianhydride.

The tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic dianhydride may be pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic acid. Dihydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic 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-decanetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, etc., but are not limited thereto.

The bismuth-based binder resin can have a weight average molecular weight of from about 1,000 grams per mole to 20,000 grams per mole, and especially from about 3,000 grams per mole to 10,000 grams per mole. When the binder-based binder resin has a weight average molecular weight within the above range, the ability to form a pattern and developability can be improved during the production of the light-shielding layer.

The acrylic-based resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer, and the first one contains at least one acrylic acid. Repeat unit resin.

a first ethylenically unsaturated monosystem-an ethylenically unsaturated monomer containing at least one carboxyl group, and examples of the monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or the like combination.

The first ethylenically unsaturated monomer may be included in an amount ranging from 5 wt% to 50 wt%, and particularly from 10 wt% to 40 wt%, based on the total amount of the acrylic resin-based resin.

The second ethylenically unsaturated monomer may comprise an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl methyl ether, etc.; an unsaturated carboxylic acid ester compound such as , (meth) methacrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (methyl Benzyl acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, etc.; mono-alkyl acrylate alkyl ester compound, such as 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth)acrylate or the like; a vinyl carboxylate compound such as vinyl acetate, vinyl benzoate or the like; a monoglycidyl glycidyl ester compound such as (methyl) A glycidyl acrylate or the like; an ethylene cyanide compound such as (meth)acrylonitrile; an unsaturated guanamine compound such as (meth) acrylamide or the like. These may be used singly or in a mixture of two or more.

Examples of the acrylic-based resin may include a copolymer of methacrylic acid/benzyl methacrylate, a copolymer of methacrylic acid/benzyl methacrylate/styrene, and a methacrylic acid/methacrylic acid benzoate. Copolymer / copolymer of 2-hydroxyethyl methacrylate, methacrylic acid / benzyl methacrylate / styrene / copolymer of 2-hydroxyethyl methacrylate, etc., but not limited thereto Wait. They may be used singly or in a mixture of two or more.

The acrylic-based resin may have a range from 3,000 g/m to 150,000 g/mole, especially 5,000 g/m to 50,000 g/mole, and more particularly 2,000 g/m to 30,000 g/m The weight average molecular weight of the ear. When the acrylic-based resin has a weight average molecular weight within this range, the photosensitive resin composition has good physical and chemical properties, proper viscosity during the production of the light-shielding layer, a column spacer, or a black spacer, and Intimate contact properties with a substrate.

The acrylic-based resin may have an acid value ranging from 15 mgKOH/g to 150 mgKOH/g, and particularly from 80 mgKOH/g to 130 mgKOH/g. When the acrylic acid-based resin has an acid value within this range, excellent pixel resolution can be achieved.

In particular, the organic binder resin may comprise a monomer having a carboxyl group (such as acrylic acid, methacrylic acid, etc.) with methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid. 2-hydroxyethyl ester, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, benzene acrylate Methyl ester, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isodecyl acrylate, isodecyl methacrylate, glycidyl methacrylate, styrene, acrylamide, acrylonitrile Copolymer, phenol novolac epoxy acrylate polymer, phenol novolac epoxy methacrylate polymer, cresol novolac epoxy acrylate polymer, cresol novolac epoxy methacrylate polymer, bisphenol A Epoxy acrylate polymer, bisphenol S epoxy acrylate polymer, and bismuth oxide propylene An acid acid addition product of an acid ester or the like.

The monomer having a carboxyl group (such as acrylic acid, methacrylic acid, etc.) may be from about 5 mol% to 50 mol%, for example, about 10 mol%, based on 100 mol% of the organic binder resin. Up to 40% of the moles are included.

The organic binder resin may have a weight average molecular weight of from about 1,000 g/m to 100,000 g/mole. When the organic binder resin has a weight average molecular weight of greater than or equal to about 1,000 grams per mole, one layer may be uniformly formed, and when the organic binder resin has a weight average molecular weight of less than or equal to about 100,000 grams per mole, Satisfactory developability.

The organic binder resin may be contained in an amount of from about 10 parts by mass to 60 parts by mass based on 100 parts by mass of the total of the organic binder resin, the photopolymerizable body, and the photopolymerization initiator. When the organic binder resin is contained in an amount of greater than or equal to about 10 parts by weight based on 100 parts by mass of the total of the organic binder resin, the photopolymerizable monomer, and the photopolymerization initiator, One layer can be easily formed during coating and drying, and the strength of this layer can be increased after curing. Further, the organic binder resin is contained in an amount of less than or equal to about 60 parts by weight based on 100 parts by mass of the solid content of the organic binder resin, the photopolymerizable monomer, and the photopolymerization initiator.

The organic binder resin may be included in an amount of from about 0.5% by weight to 20% by weight and particularly from about 1% by weight to 10% by weight based on the total solid content of the black photosensitive resin composition. When the organic binder resin is contained in this range, the viscosity can be appropriately maintained, and excellent pattern properties, processability, and developability can be achieved when a light shielding layer is formed.

Photopolymerizable monomer

The photopolymerizable monomer may be a monomer or oligomer commonly used in a black photosensitive resin composition. It may be a monofunctional or polyfunctional ester of (meth)acrylic acid containing at least one ethylenically unsaturated double bond.

Examples of the photopolymerizable monomer may include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, and 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, tripropylene methoxyethyl phosphate, hydrazine epoxy diacrylate, and the like.

Commercially available examples of the photopolymerizable monomer are as follows. Monofunctional (meth) acrylates may include Aronix M-101 ^® , M-111 ^® , M-114 ^® (TOAGOSEI CHEMICAL INDUSTRY Co., Ltd.); KAYARAD TC-110S ^® , TC-120S ^® (NIPPON KAYAKU) Co., Ltd.); V-158 ^® , V-2311 ^® (OSAKA ORGANIC CHEMICAL Ind., Ltd.), and the like. Examples of the difunctional (meth) acrylate may include Aronix M-210 ^® , M-240 ^® , M-6200 ^® (TOAGOSEI CHEMICAL INDUSTRY Co., Ltd.), KAYARAD HDDA ^® , HX-220 ^® , R- 604 ^® (NIPPON KAYAKU Co., Ltd.), V-260 ^® , V-312 ^® , V-335 HP ^® (OSAKA ORGANIC CHEMICAL Ind., Ltd.), and the like. Examples of trifunctional (meth) acrylates may include Aronix M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , M-7100 ^® , M-8030 ^® , M-8060 ^® (TOAGOSEI) CHEMICAL INDUSTRY Co., Ltd.), KAYARAD TMPTA ^® , DPCA-20 ^® , DPCA-30 ^® , DPCA-60 ^® , DPCA-120 ^® (NIPPON KAYAKU Co., Ltd.), V-295 ^® , V-300 ^® , V-360 ^® , V-GPT ^® , V-3PA ^® , V-400 ^® (Osaka Yuki Kayaku Kogyo Co. Ltd.), etc. These may be used singly or in combination of two or more.

The photopolymerizable monomer may be included in an amount ranging from about 1% by weight to 20% by weight, and particularly from about 1% by weight to 15% by weight based on the total solid amount of the black photosensitive resin composition. When the photopolymerizable monomer is contained in this range, the compatibility with the organic binder resin can be improved, and the ability to form a pattern during the production of the light shielding layer, and the sensitivity under oxygen can be improved, and A film having a smooth surface is obtained.

(D) Photopolymerization initiator

The photopolymerization initiator may be a photopolymerization initiator generally used for a black photosensitive resin composition, for example, an acetophenone-based compound, a benzophenone-based compound, and a thioxanthene. Ketone-based compound, a compound based on benzoin, one to three The main compound, a compound based on hydrazine, and the like.

Examples of the compound mainly composed of acetophenone include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and - Tert-butyltrichloroacetophenone, p-t-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl 1-(4-(methylthio)phenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylbenzene Base) - butan-1-one and the like.

Examples of benzophenone-based compounds include diphenyl Ketone, benzamidine benzoate, benzamidine benzoate methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-double ( Dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-di Chlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

Examples of thioxanthone-based compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthiophene Tons of ketone, 2-chlorothioxanthone, etc.

Examples of the compound based on benzoin include benzoin, benzoin formazan, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

Take three Examples of the main compound include 2,4,6-trichloro-s-tris, 2-phenyl 4,6-bis(trichloromethyl)-s-tris, 2-(3', 4'-di Methoxystyryl)-4,6-bis(trichloromethyl)-s-three , 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-three , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-three , 2-biphenyl 4,6-bis(trichloromethyl)-s-three , bis(trichloromethyl)-6-styryl-s-three , 2-(naphthol-yl)-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxynaphthol-yl)-4,6-bis(trichloromethyl)-s-three 2-4-bis(trichloromethyl)-6-piperidin-s-three 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-three Wait.

Examples of the ruthenium-based compound include a compound based on O-indenyl hydrazine, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2- Octanedione, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-oxime Zyrid-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, and the like. A specific example of a compound mainly composed of O-indenyl hydrazine includes 1,2-octanedione 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4) -yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butan-1,2-dione-2-indole-O-benzoate, 1-( 4-phenylsulfanylphenyl)-octane-1,2-dione-2-indole-O-benzoate, 1-(4-phenylsulfanylphenyl)-oct-1-one肟-O-acetate, and 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate.

The photopolymerization initiator may further comprise a carbazole-based compound, a diketone-based compound, a bismuth borate-based compound, a diazo-based compound, and a diimidazole-based compound. Compounds and the like.

The photopolymerization initiator may be used singly or in combination of two or more.

Since the photopolymerization initiator absorbs light and is excited, and then emits energy, it can react with a photosensitizer to cause a chemical reaction.

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

The photopolymerization initiator may be contained in an amount of about 0.1% by weight to 10% by weight, and particularly about 1% by weight to 5% by weight based on the total solid amount of the black photosensitive resin composition. When the photopolymerization initiator is contained in this range to obtain a satisfactory sensitivity of a group, the color concentration of a black photosensitive resin composition solution is appropriately maintained, and is impaired by a non-reactive initiator. Photometric deterioration can be avoided.

(E) solvent

The solvent may be a material which is compatible with, but does not react with, a lignin black-containing coloring agent, an organic binder resin, a photopolymerizable monomer, and a photopolymerization initiator.

Examples of the solvent may include alcohols such as methanol, ethanol, etc.; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran, etc.; glycol ethers such as B Glycol methyl ether, ethylene glycol ether, propylene glycol methyl ether, etc.; cyproterone acetate, such as methyl cyproterone acetate, ethyl cyproterone acetate, diethyl cyproterone acetate Ester, etc.; carbitol, such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol diethyl ether, etc.; propylene glycol alkyl ether acetates, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc.; aromatic hydrocarbons, such as toluene, two Toluene, etc.; ketones, such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl n-propyl ketone, methyl n-butyl ketone, methyl n-pentyl a ketone, a 2-heptanone or the like; a saturated aliphatic monocarboxylic acid alkyl ester such as ethyl acetate, n-butyl acetate, isobutyl acetate or the like; a lactate alkyl ester such as methyl lactate , ethyl lactate, etc.; alkyl hydroxyacetate, such as methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, etc.; alkoxyalkyl acetates, such as methoxymethyl acetate, acetic acid Methoxyethyl ester, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, etc.; alkyl 3-hydroxypropionate, such as methyl 3-hydroxypropionate, 3-hydroxyl Ethyl propionate or the like; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, Methyl 3-ethoxypropionate; etc.; alkyl 2-hydroxypropionate, such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, etc.; - alkoxypropionates such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc. ; alkyl 2-hydroxy-2-methylpropionates, such as methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, etc.; alkyl 2-alkane Oxy-2-methylpropionates, such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc. ; esters, such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutanoate, etc.; or ketoester Classes such as ethyl pyruvate and the like. In addition, the following solvents can also be used: N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-dimethyl Ethylamine, N-methylpyrrolidone, dimethyl hydrazine, benzyl ether, dihexyl ether, acetyl ketone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1- Sterol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ -butyrolactone, ethyl carbonate, propyl carbonate, phenyl cellulose Acid esters, etc. These solvents may be used singly or in combination of two or more.

Among these solvents, mutual solubility and reactivity, glycol ethers such as ethylene glycol monoethyl ether, and the like; ethylene glycol alkyl ether acetates such as ethyl cyproterone acetate and the like are considered. Esters, such as 2-hydroxyethyl propionate; diethylene glycols, such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether An acid ester or the like may be preferred.

The solvent may be contained in an amount, and particularly from about 50% by weight to 70% by weight based on the total solid content of the black photosensitive resin composition. When the solvent is contained in this range, the black photosensitive resin composition may have an appropriate viscosity, resulting in a processability improvement during the production of the light shielding layer.

(F) other additives

The photosensitive resin composition may further comprise other additives such as propylene glycol; 3-amino-1,2-propanediol; and a decane-based group having a vinyl group or a (meth) propyleneoxy group. Coupling agent; a leveling agent; a fluorine-based surfactant; a radical polymerization initiator, etc., to avoid spots or stains during coating, to achieve homogenization characteristics, and to block the residual due to the development Quality produced.

Examples of the decane-based coupling agent may include trimethoxydecyl benzoic acid, γ-methyl propylene oxypropyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ - isocyanate propyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, and the like. These may be used singly or in combination of two or more.

Examples of fluorine-based surfactants may include, for example, BM-1000 ^® , and BM-1100 ^® (BM Chemie Inc.); MEGAFACE F 142D ^® , F 172 ^® , F 173 ^® , and F 183 ^® (Dainippon Ink) Kagaku Kogyo Co., Ltd.); FULORAD FC-135 ^® , FULORAD FC-170C ^® , FULORAD FC-430 ^® , and FULORAD FC-431 ^® (Sumitomo 3M Co., Ltd.); SURFLON S-112 ^® , SURFLON S-113 ^® , SURFLON S-131 ^® , SURFLON S-141 ^® , and SURFLON S-145 ^® (Asahi Glass Co., Ltd.); and SH-28PA ^® , SH-190 ^® , SH-193 ^® , SZ Commercial products of -6032 ^® , and SF-8428 ^® (Toray Silicone Co., Ltd.).

The additives can be adjusted to suit the desired properties.

The photosensitive resin composition may further contain an epoxy compound to improve the close contact property with a substrate and the like.

Examples of the epoxy compound may include a phenol novolac epoxy compound, a tetramethylbiphenyl epoxy compound, a bisphenol A epoxy compound, a lipid cyclic epoxy compound, or a combination thereof.

The epoxy compound may be contained in an amount of from about 0.01 part by weight to 5 parts by weight, and particularly from about 0.1 part by weight to 5 parts by weight, based on 100 parts by weight of the photosensitive resin composition for a color filter. When the epoxy compound is contained in this range, excellent intimate contact properties, heat resistance, chemical resistance, and the like can be obtained.

According to another embodiment of the present invention, there is provided a light shielding layer produced using the black photosensitive resin composition.

The light shielding layer can be manufactured as follows.

(1) Coating and film formation

The photosensitive resin composition is applied onto a substrate subjected to a predetermined treatment using, for example, 0.5 μm or by a spin coating or slit coating method, a roll coating method, a screen printing method, an applicator method, or the like. The desired thickness of 25 μm. The coated substrate is then heated at a temperature ranging from about 70 ° C to 110 ° C for about 1 minute to 10 minutes to remove the solvent.

(2) exposure

The formed film is irradiated with an active ray of 190 nm to 500 nm after placing a mask having a predetermined shape to form a desired pattern. radiation It is implemented by using a light source such as a mercury lamp having a low pressure, a high pressure, or an ultrahigh pressure, a metal halide lamp, an argon laser, or the like. X-rays, electron beams, etc. can also be used as appropriate.

When a high pressure mercury lamp is used, the exposure method uses, for example, a light dose of 500 mJ/cm ₂ or less (having a 365 nm sensor). However, the light dose may vary depending on the kind of each component of the black photosensitive resin composition, the composition ratio thereof, and the dry film thickness.

(3) Development

After the exposure treatment, an aqueous alkaline solution is used to develop the exposed film by dissolving and removing unnecessary portions other than the exposed portion to form an image pattern.

(4) Post processing

The developed image pattern can be reheated or cured by an active ray radiation or the like to achieve excellent heat resistance, light resistance, close contact property, crack resistance, chemical resistance, high strength, storage stability, and the like. quality.

Therefore, the above black photosensitive resin composition can provide a pattern having improved high close contact properties and optical density required for the light shielding layer.

Another embodiment provides a color filter including the light shielding layer. The light shielding layer as above can be used for a color filter or the like.

Hereinafter, the present invention is exemplified in more detail with reference to examples. However, such examples are not to be construed as limiting the scope of the invention in any way.

(Preparation of lignin black dispersion)

A lignin black dispersion is prepared by premixing 100 grams of lignin black and 30 grams of a dispersant (BYK165) with 370 grams of one of the solvents (PGMEA) and using a 0.2 mm bead. A disperser, a new particle grinding tool (Asada Iron Works Co., Ltd.), was prepared by dispersing the mixture for about 4 hours until the dispersion particles became 100 nm.

Example 1: Preparation of a black photosensitive resin composition

A photopolymerization initiator is dissolved in a solvent, and the solution is stirred at room temperature for about 30 minutes. Here, an organic binder resin and a photopolymerizable monomer were added, and the resulting mixture was stirred for 1 hour. 60 g (54 wt%) of the lignin black dispersion was added, and the mixture was stirred for about 2 hours to obtain a solution, and this solution was filtered three times to remove impurities to prepare a black photosensitive resin composition.

Example 2: Preparation of a 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 one of lignin black dispersion and 34.6 g of one solvent were used.

Comparative Example 1: Preparation of a black photosensitive resin composition

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

Comparative Example 2: Preparation of a black photosensitive resin composition

A black photosensitive resin composition was prepared in the same manner as in Example 1, except that 100 g (60 wt%) of one of titanium sillimanite black was used. Liquid No. 1043 (MIKUNI Corp.) and 9.38 g of one solvent replaced the lignin black dispersion.

Each of the components of the black photosensitive resin composition according to Examples 1 and 2 and Comparative Examples 1 and 2 and their contents are provided in Table 1 below.

Assessment 1: Optical Density Measurement

The black photosensitive resin compositions according to Examples 1 and 2 and Comparative Examples 1 and 2 were individually spin-coated on a 0.7 mm thick glass substrate and dried on a hot plate at 90 ° C for 2 minutes, each forming about 1.0 μm thick film.

The optical density of each film was measured by using a 310TR densitometer (X-lite Co.). The results are provided in Table 2 below.

<Evaluation Reference>

○: Optical density is greater than or equal to 3.7

△: Optical density is greater than or equal to 2.5 but less than 3.7

X: Optical density is less than 2.5

Assessment 2: Resolution Measurement

Each of the films of Examples 1 to 3 and Comparative Examples 1 and 2 in Evaluation 1 was exposed to light of 40 mJ/cm ² by a broadband exposure machine having light having a peak wavelength of 365 nm. (A UV filter is equipped with a proximity exposure machine manufactured by USHIO Inc. to shield light having a wavelength of less than or equal to 350 nm). The exposed film was stabilized with a 0.04% potassium hydroxide aqueous solution at 23 ° C, and spray-developed under a spray pressure of 1.0 kg/cm ² for 60 seconds. The pattern obtained above was heated and cured in a 220 ° C oven for 30 minutes and then examined by an optical microscope. The results are provided in Table 2 below. The resolution result in Table 2 below is the minimum resolution line width.

Referring to Table 2, according to Examples 1 and 2, a lignin-containing black is contained. The black photosensitive resin composition of the colorant, an organic binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent is shown to be black photosensitive containing a conventional carbon black dispersion according to Comparative Example 1. The optical density and resolution similar to those of the resin composition, and the excellent optical density and resolution compared with the black photosensitive resin composition according to Comparative Example 2, and therefore useful as an excellent optical property and environmentally friendly The black photosensitive resin composition.

Although the present invention has been described in connection with the embodiments of the present invention, it is understood that the invention is not to be construed as limited Modification and equal configuration. Therefore, the foregoing embodiments are to be considered as illustrative and not restrictive.

Claims (10)

A black photosensitive resin composition comprising: (A) a lignin-containing coloring agent; (B) an organic binder resin; (C) a photopolymerizable monomer; (D) a photopolymerization initiator And (E) a solvent. The black photosensitive resin composition of claim 1, wherein the lignin-containing coloring agent further comprises a coloring matter, a dye, or a combination thereof. The black photosensitive resin composition of claim 1, wherein the organic binder resin has a weight average molecular weight of from 1,000 g/mol to 100,000 g/mole. The black photosensitive resin composition of claim 1, wherein the solid of the organic binder resin, the solid of the photopolymerizable monomer, and the solid of the photopolymerization initiator are based on 100 parts by mass of the total amount, The organic binder resin is contained in an amount of from 10 parts by mass to 60 parts by mass. The black photosensitive resin composition of claim 1, wherein the black photosensitive resin composition comprises: (A) 1% by weight to 60% by weight of the lignin-containing coloring agent; (B) 0.5% by weight to 20% by weight The organic binder resin; (C) 1 wt% to 10 wt% of the photopolymerizable monomer; (D) 0.1 wt% to 10 wt% of the photopolymerization initiator; (E) A balance of the solvent. The black photosensitive resin composition of claim 1, wherein the photopolymerizable monomer comprises ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, or triethylene glycol di( Methyl) acrylate, propylene glycol di(meth) acrylate, neopentyl glycol di(meth) acrylate, 1,4-butanediol di(meth) acrylate, 1,6-hexanediol (meth) acrylate, bisphenol A di(meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (methyl) ) acrylate, dipentaerythritol di(meth) acrylate, dipentaerythritol tri(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy ( Methyl) acrylate, ethylene glycol monomethyl ether (meth) acrylate, trimethylolpropane tri(meth) acrylate, tris(meth) propylene methoxyethyl phosphate, phenolic epoxy ( Methyl) acrylate, or a combination of these. The black photosensitive resin composition of claim 1, wherein the photosensitive resin composition further comprises malonic acid; 3-amino-1,2-propanediol; and one having a vinyl group or a (meth) group a decane-based coupling agent for a propylene oxide group; a homogenizing agent; a fluorine-based surfactant; a radical polymerization initiator; or a combination of the additives. The black photosensitive resin composition of claim 1, wherein the black photosensitive resin composition is used for a light shielding layer. A light-shielding layer produced by using the black photosensitive resin composition of any one of claims 1 to 8. A color filter comprising the light shielding layer of claim 9.