TWI459138B - 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 Field of invention

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

Background of the invention

It is necessary to use a black photosensitive resin composition to produce a display element of a color filter, a liquid crystal display material, an organic light emitting element (EL), a display panel material, and the like. For example, a color filter (eg, a color liquid crystal display and the like) requires a light shielding layer on the boundary between color layers (eg, red, green, blue, and the like) to enhance display. Contrast or color effect. This light shielding layer can be mainly formed of a black photosensitive resin composition.

A number of patents relating to the composition of black photosensitive resin are disclosed. Japanese Patent Laid-Open Publication No. 2002-047423 discloses that cobalt oxide is used as a black pigment to realize a black matrix having high blackness and insulating properties. Further, Japanese Patent Laid-Open Publication No. 2007-071994 uses a black matrix material comprising a monoterpene-based compound.

Recent research on a black matrix material has focused on increasing the optical density (OD) up to the maximum, but reducing the thickness of a black matrix film minimizes damage to the flatness due to the high film thickness and, therefore, in the absence of In the case of a protective film, the instillation margin of the liquid crystal is ensured.

Summary of invention

One aspect of the present invention provides a black photosensitive resin composition which has a high optical density without impairing a process, excellent patterning properties and resolution, and a low dielectric constant.

Another aspect of the present invention provides a light shielding layer which is prepared by using the black photosensitive resin composition.

According to an aspect of the present invention, there is provided a black photosensitive resin composition comprising (A) an organic binder resin; (B) a reactive unsaturated compound; (C) a photopolymerization initiator; (D) a black pigment comprising carbon black and a silver-tin alloy; and (E) a solvent, wherein the silver-containing tin alloy comprises silver and tin in a weight ratio of 6:4 to 8:2.

The carbon black and the silver-containing tin alloy may be included in a weight ratio of 1:9 to 9:1.

The black photosensitive resin composition may include 0.5 to 20% by weight of the organic binder resin (A); 1 to 20% by weight of the reactive unsaturated compound (B); 0.1 to 10% by weight of the polymerization Starting agent (C); 1 to 40 wt% of the black pigment (D) comprising carbon black and a silver-tin-containing alloy; and the solvent (E) of the difference.

The organic binder resin may include a cardo-based binder resin and the bismuth-based binder resin may be a compound containing one of the repeating units represented by the following Chemical Formula 1.

[Chemical Formula 1]

In Chemical Formula 1, R ₂₄ to R ₂₇ are the same or different, and are hydrogen, halogen, or substituted or unsubstituted C1 to C20 alkyl, R ₂₈ and R ₂₉ are the same or different, and are hydrogen. Or CH ₂ OR _a (R _a is vinyl, acryl, or methacryl), R ₃₀ is the same or different, and is hydrogen, substituted or unsubstituted C1 To C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, propylene fluorenyl, or methacryl fluorenyl, Z ₁ 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 hydrogen or substituted or unsubstituted C1 to C20 alkyl), or are represented by the following chemical formulas 2 to 12 One of the functional groups represented, Z ₂ is the same or different, and is an acid anhydride residue or an acid dianhydride residue.

[Chemical Formula 2]

[Chemical Formula 3]

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In Chemical Formula 6, R _f is hydrogen, ethyl, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH=CH ₂ , or a phenyl group.

[Chemical Formula 7]

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 12]

The bismuth-based binder resin may have a weight average molecular weight of 1,000 to 20,000 g/mol.

The silver-containing tin alloy may be included in an amount of 5 to 60% by weight based on the total solids of the black photosensitive resin composition.

The black photosensitive resin composition can be applied to a light shielding layer.

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

The light shielding layer may have an optical density of 4.0 or more at a film thickness of 0.7 μm or more.

Hereinafter, other specific examples will be described in detail.

The present invention provides a black photosensitive resin composition which has a high optical density without impairing a process, excellent patterning properties and resolution, and a low dielectric constant, which can be usefully applied to A light shielding layer.

Simple illustration

1 is a scanning electron microscope (SEM) chart showing the residue of the film pattern according to Example 1, and FIG. 2 is a scanning electron microscope (SEM) showing the residue of the film pattern according to Comparative Example 1. ) Figure.

Detailed description of the preferred embodiment

Illustrative specific examples of the present disclosure will be described in detail below. However, these specific examples are for illustrative purposes only and do not limit the disclosure.

As used herein, when a specific definition is not provided, the term "substituted" means replacing at least one hydrogen with at least one of: halogen (F, Cl, Br, or I), hydroxyl, C1 to C20 alkoxy, nitro, cyano, amine, imino, azide, methionyl, fluorenyl, fluorenylene, carbonyl, amine carbhydryl, thiol, ester, ether, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, 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 naphthenic group a combination of a C3 to C20 cycloalkenyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, or the like.

As used herein, when a specific definition is not provided, "(meth)acrylate" means both "acrylate" and "methacrylate".

The photosensitive resin composition according to a specific example includes (A) an organic binder resin, (B) a reactive unsaturated compound, (C) a photopolymerization initiator, (D) including carbon black and a a black pigment of silver tin alloy, and (E) a solvent.

(A) Organic binder resin

The organic binder resin may comprise a bismuth-based binder resin, an acryl-based binder resin, a polyimide-based binder resin, and a polyphthalate-based binder. A resin, or a combination thereof, and preferably a binder resin. The bismuth-based binder resin can improve the heat resistance and chemical resistance of the black photosensitive resin composition.

The organic binder resin may have a weight average molecular weight of 1,000 to 150,000 g/mol.

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

[Chemical Formula 1]

In Chemical Formula 1, R ₂₄ to R ₂₇ are the same or different, and are hydrogen, halogen, or substituted or unsubstituted C1 to C20 alkyl, R ₂₈ and R ₂₉ are the same or different, and are hydrogen. Or CH ₂ OR _a (R _a is vinyl, propylene fluorenyl, or methacryl fluorenyl), R ₃₀ is the same or different, and is hydrogen, substituted or unsubstituted C1 to C20 alkyl, Substituted or unsubstituted C2 to C20 alkenyl, propylene fluorenyl, or methacryl fluorenyl, Z ₁ 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 hydrogen or a substituted or unsubstituted C1 to C20 alkyl group), or one of the functional groups represented by the following Chemical Formulas 2 to 12 And Z ₂ are the same or different, and are an acid anhydride residue or an acid dianhydride residue.

[Chemical Formula 2]

[Chemical Formula 3]

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In Chemical Formula 6, R _f is hydrogen, ethyl, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH=CH ₂ , or a phenyl group.

[Chemical Formula 7]

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 12]

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

[Chemical Formula 13]

The tetracarboxylic 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'-diphenyl ether tetracarboxylic acid Dihydride, 3,3',4,4'-diphenyltetracarboxylic 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- Terpene tetracarboxylic anhydride dianhydride, 2,2-bis(3,4-dimethylphenyl)hexafluoropropane dianhydride, and the like, but not limited to them.

The bismuth-based binder resin may have a weight average molecular weight of 1,000 to 20,000 g/mol, and particularly 3,000 to 10,000 g/mol. When the bismuth-based binder resin has a weight average molecular weight within the above range, a formed light-shielding layer has excellent patterning properties and developing properties.

The propylene sulfhydryl-based binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer, and A resin comprising at least one acryl-based repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer comprising at least one carboxyl group. Examples of the monomer 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 ranging from 5 to 50% by weight, and particularly from 10 to 40% by weight, based on the total amount of the acrylonitrile-based binder resin.

Examples of the second ethylenically unsaturated monomer may include: an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl methyl ether, and the like; an unsaturated carboxyl group; Acid ester compounds, for example: methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, benzyl methacrylate, methyl Cyclohexyl acrylate, phenyl methacrylate, and the like; an aminoalkyl ester of an unsaturated carboxylic acid, such as 2-aminoethyl methacrylate or 2-dimethylaminoethyl methacrylate And analogs; carboxylic acid vinyl ester compounds, such as: vinyl acetate, vinyl benzoate, and the like; unsaturated carboxylic acid glycidyl ester compounds, such as glycidyl methacrylate, and the like; vinyl Cyanide compounds such as methacrylonitrile and the like; unsaturated guanamine compounds such as methacrylamide and the like; and the like. They can be used singly or as a mixture of more than two.

Examples of the acrylonitrile-based binder resin may include methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene copolymer, methacrylic acid/benzyl methacrylate. / 2-hydroxyethyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but not limited to them. They may be used singly or as a mixture of two or more.

The acrylonitrile-based binder resin may have a weight average molecular weight ranging from 3,000 to 150,000 g/mol, particularly a weight average molecular weight of 5,000 to 50,000 g/mol, and more particularly a weight of 2,000 to 30,000 g/mol. Average molecular weight. When the acrylonitrile-based binder resin has a weight average molecular weight within this range, the photosensitive resin composition has good physical properties and chemical properties, appropriate viscosity, and close contact with a substrate. Nature, when applied to a shading layer.

The acrylonitrile-based binder resin may have an acid value ranging from 15 to 60 mgKOH/g, and particularly an acid value of 20 to 50 mgKOH/g. When the acryl-based resin mainly has an acid value in this range, excellent pixel resolution can be achieved.

The organic binder resin may be included in an amount of 0.5 to 20% by weight, particularly 1 to 10% by weight based on the total amount of the black photosensitive resin composition. Including organic binder resins within this range, a viscosity is suitably maintained to provide a light-shielding layer having patterning properties, processability, and development properties.

(B) Reactive unsaturated compounds

The reactive unsaturated compound may be a monomer or oligomer commonly used in one of photosensitive resin compositions. It may be a monofunctional or polyfunctional methacrylate comprising at least one ethylenically unsaturated double bond.

Examples of the reactive unsaturated compound 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 methyl ether acrylate, trimethylolpropane triacrylate, tripropylene decyl oxyethyl phosphate, and the like.

Commercially available examples of such reactive unsaturated compounds are as follows. Monofunctional methacrylates can include Aronix M- , M- , M- (TOAGOSEI CHEMICAL INDUSTRY CO.,LTD.);KAYARAD TC- TC- (NIPPON KAYAKU CO.,LTD.);V- , V- (OSAKA ORGANIC CHEMICAL IND., LTD.), and the like. Examples of difunctional methacrylates may include Aronix M- , M- , M- (TOAGOSEI CHEMICAL INDUSTRY CO.,LTD.), KAYARAD HX- , R- (NIPPON KAYAKU CO.,LTD.), V- , V- V-335 (OSAKA ORGANIC CHEMICAL IND., LTD.), and the like. Examples of trifunctional methacrylates may include Aronix M- , M- , M- , M- , M- , M- , M- (TOAGOSEI CHEMICAL INDUSTRY CO.,LTD.), KAYARAD , DPCA- , DPCA- , DPCA- , DPCA- (NIPPON KAYAKU CO.,LTD.), V- , V- , V- , V- , V- , V- (Osaka Yuki Kayaku Kogyo Co., Ltd.), and the like. The reactive unsaturated compound may be used singly or as a mixture of two or more.

The reactive unsaturated compound may be included in an amount ranging from 1 to 40% by weight, and particularly 1 to 20% by weight, based on the total amount of the photosensitive resin composition. When a reactive unsaturated compound within this range is included, the compatibility with the organic binder resin is improved and thus a film can provide excellent patterning properties and sensitivity under oxygen, and The light-shielding layer has a smooth surface during its manufacture.

(C) Photopolymerization initiator

The photopolymerization initiator may be an initiator commonly used in a photosensitive resin composition, for example, an acetophenone-based compound, a diphenylketone-based compound, and a thiophene. Ketone (thioxanthone)-based compound, benzoin-based compound, three Main compounds, and the like.

The acetophenone-based compound includes 2,2'-diethoxyacetophenone, 2,2'-dibutoxyphenethyl copper, 2-hydroxy-2-methylpropiophenone (methylpropinophenone), -Third-butyltrichloroacetophenone, p-t-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2 -methyl-1-(4-(methylthio)phenyl)-2-morpholinepropan-1-one, 2-benzyl-2-dimethylamino-1-(4-? Phenylphenyl)-butan-1-one, and the like.

The diphenyl ketone-based compound includes diphenyl ketone, benzhydryl benzoate, benzoyl methyl benzoate, 4-phenyl diphenyl ketone, hydroxy diphenyl Ketone, acrylated benzophenone, 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-Dimethylaminodiphenyl ketone, 4,4'-dichlorodiphenyl ketone, 3,3'-dimethyl-2-methoxydiphenyl ketone, and the like.

Thio Ketone-based compounds including thiophenes Ketone, 2-methylthiazide Ketone, isopropyl thiophene Ketone, 2,4-diethylthio Ketone, 2,4-diisopropylthio Ketone, 2-chlorothiazide Ketones, and the like.

The benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzodimethylketal, and the like.

The three Main compounds include 2,4,6-trichloro-s-three 2-phenyl-4,6-bis(trichloromethyl)-s-three , 2-(3',4'-dimethoxystyryl)-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-(naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-s-three 2-4-trichloromethyl (sunflower based)-6-three 2-4-trichloromethyl (4'-methoxystyryl)-6-three , and the like.

The polymerization initiator may further include a carbazole-based compound, a diketone-based compound, a bismuth borate-based compound, a diazo-based compound, a bisimidazole-based compound, and the like.

Since the polymerization initiator absorbs light and amplifies and then transfers energy, it can be used with a photosensitizer to produce a chemical reaction.

The polymerization initiator may be included in an amount of 0.01 wt% to 10 wt%, and particularly an amount of 0.1 to 5 wt%, based on the total amount of the black photosensitive resin composition. When the photopolymerization initiator in this range is included, the sensitivity of the radical is good, a solution of the black photosensitive resin composition has a desired color density, and the transmittance is lowered due to the non-reactive initiator. Can be suppressed.

(D) black pigment

The black pigment may be a carbon black and a mixed pigment containing a silver tin alloy.

The carbon black may not be particularly limited but includes, in particular, graphitized carbon, furnace black, acetylene black, ketjen black, and the like.

The silver-containing tin alloy may include silver (Ag) and tin (Sn) as main components and an average particle size ranging from 1 to 300 nm and, in particular, from 1 to 10 nm. When a silver-containing tin alloy having an average particle size within this range, it is possible to prevent fine impurities from being generated on a substrate during the pattern forming process.

The silver-containing tin alloy may be a black pigment. Here, silver and tin may have a weight ratio ranging from 6:4 to 8:2 and, in particular, a weight ratio ranging from 7:3 to 7.5:2.5. When silver and tin have an alloy ratio in this range, a light-shielding layer can have a higher optical density, excellent light-blocking properties, and appropriate conductivity, and thus the dielectric constant can be easily controlled.

The silver-containing tin alloy may be coated to have an insulating layer on the surface. The coating can be carried out by using a compound based on a vermiculite. The coated silver-containing tin alloy can be easily dispersed in a solvent and impart an optical density to a light-shielding layer.

The carbon black and the silver-containing tin alloy may be mixed in a weight ratio ranging from 1:9 to 9:1 and, in particular, from 1:1 to 1:8. When they are used at this ratio, they or the like can bring about high optical density as well as excellent workability such as patterning properties, resolution, and the like.

The silver-containing tin alloy may be included in an amount of 1 to 60% by weight and, in particular, in an amount of 30 to 60% by weight based on the total amount of solids of the black photosensitive resin composition. When a silver-containing tin alloy in this range is included, it can bring high optical density without impairing workability, that is, development edge, exposure edge, resolution, and the like in a light shielding layer. During preparation.

When the black pigment is mixed with a dispersing agent, a solvent, and the like to prepare a pigment dispersion solution, it can be used for the black photosensitive resin composition. Specifically, the silver-containing tin alloy is mixed with a dispersant, a solvent, and the like to prepare a first dye dispersion solution, and the carbon black is mixed with a dispersant, a solvent, and the like to A second pigment dispersion solution is prepared. Then, the first and second dye dispersion solutions are mixed together and used for the black photosensitive resin composition. Otherwise, the silver-containing tin alloy is mixed with a carbon black while being mixed with a dispersing agent, a solvent, and the like to prepare a pigment dispersion solution. The pigment dispersion solution can be used for the black photosensitive resin composition.

The dispersant assists in the uniform dispersion of the black pigment in the solvent.

The dispersing agent may include a nonionic compound, an anionic compound, a cationic compound, or a combination thereof. Examples of the dispersant include polyalkylene glycol and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide addition product, alcohol alkylene oxide addition product, sulfonate, sulfonate Carboxylic esters, carboxylates, alkylguanamine alkylene oxide addition products, alkylamines, and the like.

Commercially available examples of such dispersants are as follows: DISPERBYK-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 (BYK); EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100 EFKA-400, EFKA-450, and the like (EFKA chemicals); Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, and the like (Zeneka) Or PB711, PB821, and the like (Ajinomoto).

The dispersant may be included in an amount of 0.01 to 15% by weight based on the total amount of the black photosensitive resin composition. When the dispersant in the above range is included, the dispersion of the black photosensitive resin composition is improved to cause excellent stability, development properties, and patterning properties during the production of a light shielding layer.

This solvent is explained below.

The black pigment may be included in an amount of 1 to 40% by weight, and particularly 5 to 30% by weight based on the total amount of the black photosensitive resin composition. When a black pigment in the above range is included, a light-shielding layer having excellent insulating properties, high optical density, and excellent developing property and workability is provided.

(E) solvent

The solvent has compatibility with the organic binder resin, the reactive unsaturated compound, the photopolymerization initiator, and the black pigment, but does not have a reaction therewith.

Examples of the solvent may include alcohols such as methanol, ethanol, and the like; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran, and the like; glycol ethers, For example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the like; acetaminophen acetate, for example: acesulfame acetate, acesulfame acetate, dicetaxel acetate, and the like; Alcohol, for example: methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol methyl ethyl ether, two Ethylene glycol ethyl ether or the like; propylene glycol alkyl ether acetate, for example: propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, and the like; aromatic hydrocarbons such as toluene, xylene, and the like; ketones, for example : methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-acetone, methyl-n-butanone, methyl-n-pentanone, 2-heptanone, and Analogs; saturated aliphatic monocarboxylic acid alkyl esters, for example: ethyl acetate, n-butyl acetate, isobutyl acetate, and the like; lactate esters, for example: lactate A , ethyl lactate, and the like; alkyloxy acetate, such as: methyloxyacetate, ethyloxyacetate, butyloxyacetate, and the like; alkylalkane Oxyacetic acid esters, for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and the like; 3-oxygen 3-oxy propionate alkylesters, such as methyl 3-oxypropionate, ethyl 3-oxypropionate, and the like; alkyl 3-alkoxypropionate, for example: Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, and the like; 2-oxypropionic acid Alkyl esters, for example: methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxy propionic acid propyl, and the like; 2-alkoxy Alkyl propionate, for example: methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, and the like 2-oxy-2-methylpropionate, for example: methyl 2-oxy-2-methylpropanoate, 2-oxy-2-methylpropane Ethyl ethyl ester, and the like; alkoxy monoalkyl monocarboxylic acid alkyl ester of 2-alkoxy-2-methylpropionic acid alkyl group, for example: methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropanoate, and the like; esters, for example: ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, 2 Methyl hydroxy-3-methylbutanoate, and the like; a series of ketonate esters such as ethyl pyruvate, and the like. Further, the following high boiling solvents may be further added: N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N, N- Dimethylacetamidine, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetamidine, isophorone, caproic acid, octanoic acid, 1-octanol, 1-nonanol , benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, cyanoacetate, and the like .

In view of mutual solubility and reactivity, glycol ethers such as ethylene glycol monoethyl ether, and the like; ethylene glycol alkyl ether acetates, for example, ethyl acetate, and the like; esters, such as 2- Ethyl hydroxypropionate, and the like; carbitol, such as diethylene glycol monomethyl ether, and the like; propylene glycol alkyl ether acetate, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, And similar.

The solvent is used as a difference, and particularly 50 to 70% by weight based on the total amount of the black photosensitive resin composition. When the solvent in this range is included, the black photosensitive resin composition may have an appropriate viscosity to cause an improvement in workability of a light shielding layer.

(F) Other additives

The black photosensitive resin composition may further include a decane coupling agent having a reactive substituent such as a carboxyl group, a methacryl oxime group, an isocyanate group, an epoxy group, and the like to improve adhesion to a substrate.

Examples of the decane coupling agent include trimethoxy sulfonyl benzoic acid, γ-methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, and γ-isocyanatopropyl three. Ethoxy decane, γ-glycidyloxypropyl trimethoxy decane, β-(3,4-ethoxycyclohexyl)ethyltrimethoxydecane, and the like. They may be used singly or as a mixture of two or more.

The decane coupling agent may be included in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the organic binder resin.

The black photosensitive resin composition may further include a surfactant 俾 to improve coating properties and suppress spots.

Examples of the surfactant may include a fluorine-based surfactant, for example, BM- , and BM- (BM Chemie Inc.); MEGAFACE F , F , F With F DAINIPPON INK KAGAKU KOGYO CO.,LTD.);FULORAD FC- , FULORAD FC- , FULORAD FC- With FULORAD FC- (SUMITOMO 3M CO., LTD.); SURFLON S- , SURFLON S- , SURFLON S- , SURFLON S- With SURFLON S- (ASAHI GLASS CO., LTD.); and SH- , SH- , SH- , SZ- With SF- , and the like (TORAY SILICONE CO., LTD.).

The surfactant may be included in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the organic binder resin. When a surfactant in this range is included, coating uniformity can be ensured without staining, and the wetting property of a glass substrate is improved.

The black photosensitive resin composition may further contain other additives, for example, an antioxidant, a stabilizer, and the like in a predetermined amount, when they lower the properties.

According to another specific example, a light shielding layer produced using the photosensitive resin composition is provided. The light shielding layer can be manufactured as follows.

(1) Application and film formation

The aforementioned black photosensitive resin composition is coated with a spin coating method or a slit coating method, a roll coating method, a screen printing method, an applicator method, and the like to have a desired thickness. For example, a range of from 0.9 to 1.5 μm is applied to one of the pretreated substrates, and, in turn, heated at a temperature ranging from 70 to 90 ° C for 1 to 10 minutes to remove a solvent.

The film has an optical density of more than 4.0 at a thickness of 0.7 μm. It has a higher optical density, which is better. When the black photosensitive resin composition has an optical density within this range, light from the bottom may not be irradiated.

(2) exposure

A mask is placed on the prepared film to form a pattern. Membrane-coated membranes are irradiated with active radiation ranging from 200 to 500 nm. The radiation is performed by using a light source such as a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon laser, and the like. However, the light source can include an X-ray, an electron beam, and the like, depending on the condition.

The exposure may use a light dose of 500 mJ/cm ² or less (by a 365 nm sensor) accompanied by a high pressure mercury lamp, but depending on the type of the component contained in the black photosensitive resin composition, the combination ratio thereof, The combined amount of these, as well as the thickness of a dry layer, varies.

(3) Development

The exposed film is developed with an aqueous alkaline solution to dissolve and remove unnecessary portions but retain the exposed portions to form an image pattern.

(4) Post process

The developed image pattern can be heated or irradiated with an active ray for curing to achieve excellent heat resistance, photoresist resistance, tight contact properties, crack resistance, chemical resistance, high strength, storage stability, and the like. .

The aforementioned black photosensitive resin composition can bring about excellent insulating properties and optical densities required for a light shielding layer.

In the following, the invention is explained in more detail with reference to the examples. However, these are exemplary embodiments of the invention and are non-limiting.

Examples 1 to 4 and Comparative Examples 1 to 5

Each of the black photosensitive resin compositions according to Examples 1 to 4 and Comparative Examples 1 to 5 was prepared to have the composition shown in Table 1 using the following components.

(A) Organic binder resin

(A-1) 159 g of 3,3-bis(4-hydroxyphenyl)-2-benzofuran-1-one, 426.6 g of epichlorohydrin, and 160 g of a 50% aqueous alkaline solution in a 1 L flask The mixture was mixed and then reacted at 95 ° C for 1 hour to obtain a bisphenylbenzofuran type epoxy resin. 215 g of a bisphenylbenzofuran type epoxy resin was mixed with 450 mg of triethylbenzylammonium chloride, 100 mg of 2,6-diisobutylphenol, and 72 g of acrylic acid. The mixture is heated and completely dissolved at a temperature ranging from 90 to 120 ° C, while the air system is 25 m per minute. The speed is blown into it. Next, the resulting product was cooled to room temperature to prepare an achromatic transparent solid bisphenylbenzofuran type epoxy acrylate. 287 g of the synthesized bisphenylbenzofuran type epoxy acrylate was dissolved in 2 kg of ceramide acetate. Next, 38 g of 1,2,3,6-tetrahydrophthacid anhydride, 80.5 g of benzophenone tetracarboxylic dianhydride, and 1 g of bromine Tetraethylammonium is added to the solution. The mixture was slowly heated for the reaction up to 110 to 115 ° C for 2 hours to prepare a binder resin having a weight average molecular weight of 5,000 g/mol.

(A-2) 159 g of 3,3-bis(4-hydroxyphenyl)-2-benzofuran-1-one, 426.6 g of epichlorohydrin, and 160 g of a 50% aqueous alkaline solution in a 1 L flask The mixture was mixed and heated at 95 ° C for 1 hour to obtain a bisphenylbenzofuran type epoxy resin. 215 g of a bisphenylbenzofuran type epoxy resin was mixed with 450 mg of triethylbenzylammonium chloride, 100 mg of 2,6-diisobutylphenol, and 72 g of acrylic acid. Heat the mixture to 90 to 120 ° C and dissolve completely, while the air is 25M The speed is blown into it. Next, the dissolved product was cooled to room temperature to prepare an achromatic transparent solid bisphenylbenzofuran type epoxy acrylate. 287 g of the synthesized bisphenylbenzofuran type epoxy acrylate was dissolved in 2 kg of ceramide acetate. The solution is combined with 10 g of 1,2,3,6-tetrahydrophthacid anhydride, 108.5 g of benzophenone tetracarboxylic dianhydride, and 1 g of bromination. Tetraethylammonium is mixed. The mixture was slowly heated to 110 to 115 ° C for 2 hours to prepare a binder resin having a weight average molecular weight of 30,000 g/mol.

(B) Reactive unsaturated compounds

Dipentaerythritol hexaacrylate was used.

(C) Photopolymerization initiator

IGR 369 manufactured by Ciba-Geigy Co. was used.

(D) Black pigment dispersion

(D-1) using a pigment dispersion including a silver tin alloy (TMP-DC-1, pigment solid = 30%, weight ratio between silver and tin = 7:3, Sumitomo Osaka Cement Co., Ltd.) Solution.

(D-2) A pigment dispersion solution (C1-M-050, Sakata Co.) including carbon black was used.

(E) solvent

Propylene glycol methyl ether acetate was used.

(F) Other additives

Γ-glycidyloxypropyltrimethoxydecane (S-510, Chisso Co.) was used as a decane coupling agent.

Evaluation 1-optical density

The black photosensitive resin compositions according to Examples 1 to 4 and Comparative Examples 1 to 5 were separately coated on a 0.7 mm-thick glass substrate and connected to a 90 ° C heating plate. Drying was carried out for 2.5 minutes to produce a 0.7 μm-thick film. The film was cooled to room temperature and forced to dry in a convection drying oven at 230 ° C for 30 minutes. In turn, each film was measured for optical density by using a 310TR optical densitometer (X-lite Co.). The results are provided in Table 2 below.

<Evaluation Reference>

○: optical density of more than 4

△: optical density ranging from 2.5 to 4.0

×: optical density less than 2.5

Evaluation 2 - Determination of pattern formation properties

Each of the films obtained in Evaluation 1 according to Examples 1 to 4 and Comparative Examples 1 to 5 was covered with a pattern mask and irradiated with a wavelength of 365 nm at 40 mJ/cm ² . The resulting product was developed with an aqueous solution diluted with 1 wt% potassium hydroxide at 23 ° C for 1 minute and then rinsed with pure water for 1 minute. The obtained pattern was heated and cured in a 220 ° C oven for 30 minutes and then examined using an optical microscope. The results are provided in Table 2 below and Figures 1 and 2.

Fig. 1 is a scanning electron microscope (SEM) chart showing the pattern of the film according to Example 1. Fig. 2 is a scanning electron microscope (SEM) chart showing the pattern of the film according to Comparative Example 1.

<Evaluation Reference>

○: Good formation of a 10 μm pattern

△: poor formation of 10 μm pattern

×: 10 μm pattern is not formed

Evaluation 3-resolution measurement

Each of the patterns obtained in Evaluation 2 according to Examples 1 to 4 and Comparative Examples 1 to 5 was examined with an optical microscope for the smallest pattern. The results are provided in Table 2 below. The resolution measurements in Table 2 below indicate the pattern size of a mask used during exposure and are measured by using VK-8550 manufactured by KEYENCE Co.

Evaluation of 4-dielectric constant

The black photosensitive resin compositions according to Examples 1 to 4 and Comparative Examples 1 to 5 were each used separately to prepare a light shielding layer. Here, as for the substrate, an ITO (Indium Tin Oxide) glass was used. The lower substrate is partially disposed with a light shielding layer, but exposes the ITO to the remaining portion. Then, a gold (Au) electrode was sputtered onto the prepared sample. The resulting product is calculated by measuring the capacitance using an LCR meter device to calculate its dielectric constant. The results are provided in Table 2 below.

Referring to Table 2, according to Examples 1 to 4, an organic binder resin, a reactive unsaturated compound, a photopolymerization initiator, a black pigment including carbon black and a silver-tin-containing alloy, and a solvent are included. The black photosensitive resin composition has excellent resolution or excellent pattern forming properties and optical density, as compared with any of the black pigments according to Comparative Examples 1 to 5, including any of carbon black or silver-containing tin alloy. Wait.

In particular, the black photosensitive resin composition including only carbon black according to Comparative Example 1 had deteriorated pattern formation properties, resolution, and dielectric constant as compared with those according to Examples 1 to 4. The black photosensitive resin composition including only a silver-tin alloy according to Comparative Examples 2 to 5 had very deteriorated pattern forming properties. Further, referring to Figs. 1 and 2, the film of Example 1 had a pattern better than that of Comparative Film of Example 1.

Further, the black photosensitive resin composition containing silver tin alloy included in the range according to Comparative Example 2 has deteriorated pattern forming properties and optical density, compared with 5 to 4 in accordance with Examples 1 to 4 60 wt% of an amount (based on the total amount thereof) of such a silver-containing tin alloy.

Further, the black photosensitive resin composition comprising the binder resin mainly comprising one of the weight average molecular weights ranging from 1,000 to 20,000 g/mol according to Comparative Example 2 has a better resolution, compared with the basis The third embodiment includes the bismuth-based binder resin outside the range.

Although the present disclosure has been described in what is considered as a practical illustrative embodiment, it is understood that the invention is not limited to the specific examples disclosed, but rather, the scope and scope of the accompanying claims Various modifications and equivalent configurations within. The foregoing specific examples are illustrative but not limiting in any way.

Figure 1 is a scanning electron microscope (SEM) image showing the residue of the film pattern according to Example 1;

Fig. 2 is a scanning electron microscope (SEM) chart showing the residue of the film pattern according to Comparative Example 1.

Claims (9)

A black photosensitive resin composition comprising (A) an organic binder resin; (B) a reactive unsaturated compound; (C) a photopolymerization initiator; (D) a carbon black and a a black pigment of silver tin alloy; and (E) a solvent, wherein the silver-containing tin alloy comprises silver and tin in a weight ratio of 6:4 to 8:2, and the carbon black and the silver-containing tin alloy are 1: A weight ratio of 8 to 1:1 is included. The black photosensitive resin composition of claim 1, wherein the black photosensitive resin composition contains 0.5 to 20% by weight of the organic binder resin (A); and 1 to 20% by weight of the reactive unsaturated compound ( B); 0.1 to 10% by weight of the photopolymerization initiator (C); 1 to 40% by weight of the black pigment (D) containing carbon black and a silver-tin-containing alloy; and the solvent (E). The black photosensitive resin composition of claim 1, wherein the organic binder resin comprises a cardo-based binder resin. The black photosensitive resin composition of claim 3, wherein the bismuth-based binder resin comprises a compound containing a re-fraction unit represented by the following Chemical Formula 1: Wherein, in Chemical Formula 1, R ₂₄ to R ₂₇ are the same or different, and are hydrogen, halogen, or a substituted or unsubstituted C1 to C20 alkyl group, and R ₂₈ and R ₂₉ are the same or different, and Is hydrogen or CH ₂ OR _a (R _a is vinyl, propylene fluorenyl, or methacryl fluorenyl), R ₃₀ is the same or different, and is hydrogen, substituted or unsubstituted C1 to C20 alkyl , substituted or unsubstituted C2 to C20 alkenyl, propylene fluorenyl, or methacryl fluorenyl, Z ₁ being the same or different and being a single bond, O, CO, SO ₂ , CR _b R _c , SiR _d R _e (wherein R _b to R _e are the same or different, and are hydrogen or a substituted or unsubstituted C1 to C20 alkyl group), or a functional group represented by the following Chemical Formulas 2 to 12 In one case, and Z ₂ is the same or different, and is an acid anhydride residual group or an acid dianhydride residue group, [Chemical Formula 3] Wherein, in Chemical Formula 6, R _f is hydrogen, ethyl, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH=CH ₂ , or phenyl, [Chemical Formula 8] The black photosensitive resin composition of claim 3, wherein the bismuth-based binder resin has a weight average molecular weight of 1,000 to 20,000 g/mol. For example, the black photosensitive resin composition of claim 1 of the patent scope, wherein The silver-containing tin alloy may be included in an amount of 5 to 60% by weight based on the total solids of the black photosensitive resin composition. The black photosensitive resin composition of claim 1, wherein the black photosensitive resin composition is applied to a light shielding layer. A light-shielding layer produced by using the black photosensitive resin composition according to any one of claims 1 to 7. The light-shielding layer of claim 8, wherein the light-shielding layer has an optical density of 4.0 or more at a film thickness of 0.7 μm or more.