KR101720718B1 - Photosensitive resin composition for light blocking layer and light blocking layer using the same - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기는 명세서에 정의된 바와 같다.)(B) a binder resin, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, and (E) a solvent, wherein the colorant comprises (A) a colorant comprising a blue- A photosensitive resin composition for a light-shielding layer, and a light-shielding layer using the same.
[Chemical Formula 1]

(Wherein each substituent is as defined in the specification).

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition for a light-shielding layer and a light-shielding layer using the same. BACKGROUND ART [0002]

The present invention relates to a photosensitive resin composition for a light-shielding layer and a light-shielding layer using the same.

The light-sensitive resin composition for a light-shielding layer is an indispensable material for the production of display elements such as a light-shielding layer, a liquid crystal display material, an organic light emitting element (EL), and a display panel material. For example, in the light-shielding layer of a color liquid crystal display or the like, a light-shielding layer is required at a boundary portion between colored layers such as red, green, and blue in order to improve display contrast and coloring effect, The light-shielding layer is mainly formed of a photosensitive resin composition for a light-shielding layer.

Since the carbon pigment-dispersed photosensitive composition frequently used at present has a low electrical resistance, it is difficult to use it as a photo-spacer or an insulating material. Accordingly, Japanese Patent No. 2,552,391 uses an insulating organic pigment comprising a mixed organic pigment in place of carbon black in order to realize a material having a high degree of insulation while having a high degree of insulation such as a photo spacer. However, in this case, the optical density (OD) value is lowered by using only the organic pigment.

An embodiment of the present invention is to provide a photosensitive resin composition for a light-shielding layer which is excellent in light shielding property and prevents metal ion elution.

Another embodiment of the present invention is to provide a light-shielding layer produced using the photosensitive resin composition for a light-shielding layer.

One embodiment of the present invention is a coloring agent comprising (A) a coloring agent comprising a blue-based material and a red-based material including a dye represented by the following formula (1); (B) a binder resin; (C) a photopolymerizable monomer; (D) a photopolymerization initiator; And (E) a solvent, wherein the blue-based material does not contain a metal ion.

[Chemical Formula 1]

(In the formula 1,

X ¹ and X ² are each independently a carbon atom, a sulfur atom or an oxygen atom,

R ¹ to R ⁶ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 A substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 hetero A substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,

The Y ¹ ring group and the Y ² ring group are each independently a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, A substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group, RTI ID = 0.0 > C2-C30 < / RTI > heteroaryl group,

A ¹ represents a halogen anion, a perhalogenated anion, a tetrafluoroborate anion (BF ₄ ^- ), a hexafluoroantimonate anion (SbF ₆ ^- ), a haloacetate anion, an alkylsulfate anion, a sulfonate anion or a hexafluoro Phosphate anion (PF < ₆ > ^- )

and n ¹ to n ⁴ are each 0 or 1.)

The dye represented by the formula (1) may be a dye represented by the following formula (2).

(2)

(In the formula (2)

R ⁷ to R ¹² each independently represent a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 A substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 hetero A substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,

A ² represents a halogen anion, a perhalogenated anion, a tetrafluoroborate anion (BF ₄ ^- ), a hexafluoroantimonate anion (SbF ₆ ^- ), a haloacetate anion, an alkylsulfate anion, a sulfonate anion or a hexafluoro Phosphate anion (PF ₆ ^- ).

The blue-based material may further include a violet pigment.

The red-based material may include a dye, a pigment, or a combination thereof.

Wherein the red material is at least one selected from the group consisting of a perylene pigment, an anthraquinone pigment, a giant lake quinone pigment, an azo pigment, a diazo pigment, a quinacridone pigment, an anthracene pigment, .

The colorant may include the blue-based material and the red-based material at a weight ratio of 10:90 to 90:10.

The colorant may further include a green-based material.

The green-based material may comprise a dye, a pigment, or a combination thereof.

The green-based material may include a halogenated phthalocyanine-based pigment.

The light-sensitive resin composition for a light-shielding layer contains 1 to 80% by weight of the colorant (A); 0.1 to 30% by weight of the binder resin (B); 0.1 to 30% by weight of the (C) photopolymerizable monomer; 0.1 to 5% by weight of the photopolymerization initiator (D); And (E) the solvent balance.

Another embodiment of the present invention provides a light-shielding layer produced using the photosensitive resin composition for a light-shielding layer.

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

The light shielding layer is excellent in light shielding property and excellent in reliability due to prevention of elution of metal ions.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless otherwise specified herein, "substituted" means that at least one hydrogen atom in the compound is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, A thio group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an acid anhydride, an amide group, an azo group, an azido group, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, , 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 C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, An alkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, or a combination thereof.

Unless otherwise stated, the terms "heterocycloalkyl", "heterocycloalkenyl", "heterocycloalkynyl" and "heterocycloalkylene" refer to cycloalkyl, cycloalkenyl, cycloalkynyl, and cycloalkyl Means that at least one heteroatom of N, O, S or P is present in the ring compound of the ring.

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

The photosensitive resin composition for a light-shielding layer may contain (A) a colorant, (B) a binder resin, (C) a photopolymerizable monomer, (D) a photopolymerization initiator and (E) a solvent.

Each component will be described in detail below.

(A) Colorant

The colorant according to one embodiment may be used by mixing a blue-based material and a red-based material.

The blue-based material may be a dye represented by the following formula (1), which does not contain a metal ion.

[Chemical Formula 1]

(In the formula 1,

X ¹ and X ² are each independently a carbon atom, a sulfur atom or an oxygen atom,

R ¹ to R ⁶ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 A substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 hetero A substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,

The Y ¹ ring group and the Y ² ring group are each independently a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, A substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group, RTI ID = 0.0 > C2-C30 < / RTI > heteroaryl group,

A ¹ represents a halogen anion, a perhalogenated anion, a tetrafluoroborate anion (BF ₄ ^- ), a hexafluoroantimonate anion (SbF ₆ ^- ), a haloacetate anion, an alkylsulfate anion, a sulfonate anion or a hexafluoro Phosphate anion (PF < ₆ > ^- )

and n ¹ to n ⁴ are each 0 or 1.)

In the formula (1), when X ¹ and X ² are each a sulfur atom or an oxygen atom, n ¹ to n ⁴ are each 0.

The blackness can be realized by mixing the blue-based material such as the dye represented by Formula 1 and the red-based material, and the use of the blue-based material not containing the metal ion allows the dissolution of the metal ion by the solvent Does not occur. Further, since the use of carbon black is substituted for the photosensitive resin composition, blackness can be realized while having high insulation.

The dye represented by the formula (1) may be a dye represented by the following formula (2).

(2)

(In the formula (2)

R ⁷ to R ¹² each independently represent a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 A substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 hetero A substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,

A ² is a halogen anion; Perhalogenated anions such as ClO ₄ ^- ; Tetrafluoroborate anion (BF ₄ ^- ); Hexafluoroantimonate anion (SbF ₆ ^- ); A haloacetate anion such as CF ₃ CO ₂ ^- ; Alkyl sulfate anion; N (SO ₂ CF ₃ ) ₂ ^- , sulfonic acid salt anions such as the anions represented by the following formulas (3-1) and (3-2); Or a hexafluorophosphate anion (PF ₆ ^- ).)

[Formula 3-1]

[Formula 3-2]

More specific examples of the dyes represented by the formula (1) include dyes represented by the following formula (4), but the present invention is not limited thereto.

[Chemical Formula 4]

The blue-based material may be a violet pigment in addition to the dye represented by the above-mentioned formula (1).

Examples of the violet pigment include GeoKi Photo Violet Sat, First Violet B, Methyl Violet Toyoki, Indanthrene Violet Rain Violet and the like.

The red material may be a dye, a pigment, or a combination thereof. Specific examples thereof include a perylene pigment, an anthraquinone pigment, a giant lake quinone pigment, an azo pigment, a diazo pigment, quinacridone ) Based pigments, anthracene based pigments, or a combination thereof. More specific examples of the red material include perylene pigments, quinacridone pigments, naphthol AS, siccone pigments, anthraquinone (sudan I, II, III, R), giant tracino Nilets also include vis azo, benzopyran, and the like.

The blue-based material and the red-based material may be mixed in a weight ratio of 10:90 to 90:10, specifically, in a weight ratio of 60:40 to 90:10, and more specifically, 85:15 by weight. When the mixture is used within the above weight ratio range, blackness can be realized.

In addition to the blue-based material and the red-based material, the colorant may be used by mixing together a green-based material.

The green-based material may be a dye, a pigment, or a combination thereof. Specifically, a halogenated phthalocyanine-based pigment may be used. More specific examples of the green-based material include polychloro-copper phthalocyanine, polychlorobromophthalocyanine, and the like.

The pigments may be included in the photosensitive resin composition for a light-shielding layer in the form of a dispersion. Such a pigment dispersion may be composed of the pigment, a solvent, a dispersing agent, a binder resin, and the like.

As the solvent, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether and the like can be used. Among them, propylene glycol methyl ether acetate is preferably used .

The dispersant helps to uniformly disperse the pigment in the dispersion, and any nonionic, anionic or cationic dispersant may be used. Specific examples thereof include polyalkylene glycols or esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, carboxylic acid salts, alkylamide alkylene oxide adducts Water, alkylamine, and the like. These may be used alone or in combination of two or more.

The binder resin may use an acrylic resin including a carboxyl group, which not only improves the stability of the pigment dispersion but also improves the patterning of pixels.

The primary particle diameter of the pigment may be 10 to 70 nm. When the primary particle diameter of the pigment is within the above range, the stability in the pigment dispersion is excellent and the resolution of the pixel is also excellent.

The secondary particle diameter of the pigment is not particularly limited, but may be 200 nm or less, in particular 70 nm to 100 nm, considering the resolution of the pixel. Esters, carboxylic acid salts, alkylamide alkylene oxide adducts, and alkylamines. These may be used alone or in admixture of two or more.

The colorant may be contained in an amount of 1% by weight to 80% by weight based on the total amount of the photosensitive resin composition for the light-shielding layer, and specifically 50% by weight to 70% by weight. When the colorant is used within the above range, it is possible to obtain a light-shielding layer which can realize blackness and is excellent in reliability.

(B) binder resin

The binder resin may be a carcass binder resin, an acrylic binder resin, a polyimide binder resin, a polyurethane binder resin, or a combination thereof.

The weight average molecular weight of the binder resin may be from 1,000 g / mol to 150,000 g / mol.

Among the above-mentioned kinds of the binder resin, the cadmium-based binder resin can be preferably used. When the cationic binder resin is used, the heat resistance and chemical resistance of the photosensitive resin composition can be improved.

The weight average molecular weight of the cationic binder resin may be from 1,000 g / mol to 50,000 g / mol, and specifically from 3,000 g / mol to 35,000 g / mol. When the weight average molecular weight of the cationic binder resin is within the above range, excellent patterning property and developability can be obtained in the production of the light-shielding layer.

The cadmium binder resin may be a compound containing a repeating unit represented by the following formula (5).

[Chemical Formula 5]

(In the above formula (5)

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

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

R ₃₀ is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, an acrylate group or a methacrylate group,

Z ₁ is a single bond, O, CO, SO ₂ , CR _b R _c , SiR _d R _e (wherein R _b to R _e are the same or different and are a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group Or a compound represented by any one of the following formulas (6) to (16)

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

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(In the formula (10)

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.

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

The cadmium binder resin can be specifically obtained by reacting a compound represented by the following formula (17) with a tetracarboxylic acid dianhydride.

[Chemical Formula 17]

The tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic acid dianhydride include pyromellic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4-biphenyltetracarboxylic dianhydride, 2 , 2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic acid dianhydride , 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid 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-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylene Tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, and the like, but the present invention is not limited thereto.

The acrylic binder resin may contain a first ethylenic unsaturated monomer And a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin comprising at least one acrylic repeating unit.

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

The first ethylenically unsaturated monomer may be contained in an amount of 5% by weight to 50% by weight based on the total amount of the acrylic binder resin, specifically, 10% by weight to 40% by weight.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene,? -Methylstyrene, vinyltoluene, or vinylbenzyl methyl ether; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; A vinyl cyanide compound such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These may be used singly or in combination of two or more.

Specific examples of the acrylic binder resin 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, but are not limited thereto, and they may be used alone or in combination of two or more.

The acrylic binder resin may have a weight average molecular weight of from 3,000 g / mol to 150,000 g / mol, specifically from 5,000 g / mol to 50,000 g / mol, more specifically from 2,000 g / mol to 30,000 g / mol. 　 When the weight average molecular weight of the acrylic binder resin is within the above range, the photosensitive resin composition for a light-shielding layer is excellent in physical and chemical properties, has an appropriate viscosity, and is excellent in adhesion to a substrate in the production of a light- shielding layer.

The acid value of the acrylic binder resin may be from 15 mgKOH / g to 60 mgKOH / g, and specifically from 20 mgKOH / g to 50 mgKOH / g. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern is excellent.

The binder resin is preferably added to the total amount of the photosensitive resin composition for the light- 　 0.1% by weight to 30% by weight, and specifically, 　 1% by weight to 20% by weight. When the binder resin is contained within the above range, the viscosity is appropriately maintained, and the patterning property, the processability, and the developing property are excellent when the light-shielding layer is produced.

(C) Photopolymerization  Monomer

As the photopolymerizable monomer, a polyfunctional monomer having two or more hydroxyl groups may be used. Specific examples of the photopolymerizable monomer include glycerol acrylate, dipentaerythritol hexaacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol acrylate, pentaerythritol hexaacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, But are not limited to, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate , 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate Acrylate and the like.

The photopolymerizable monomer may be contained in an amount of 0.1% by weight to 30% by weight based on the total amount of the photosensitive resin composition for a light-shielding layer, and specifically 5% by weight to 20% by weight. When the photopolymerizable monomer is contained within the above range, the pattern characteristics and developability are excellent in the production of the light-shielding layer.

(D) Light curing Initiator

The photopolymerization initiator is a photopolymerization initiator generally used in a photosensitive resin composition. Examples of the photopolymerization initiator include an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, a oxime compound, Can be used.

Examples of the acetophenone compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, Dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane- 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Orcanthon and the like can be used.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the triazine type compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) -s- triazine, 2- (3 ', 4'-dimethoxy (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho 1-yl) -4,6-bis 6-triazine, 2-4-trichloromethyl (4'-methoxystyryl) -6-triazine, and the like can be used.

Examples of the oxime compounds include 1,2-octanedione, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone.

In addition to the above-described photopolymerization initiators, carbazole-based compounds, diketone compounds, sulfonium borate compounds, diazo compounds, and imidazole-based compounds can also be used as a photopolymerization initiator.

The photopolymerization initiator may be contained in an amount of 0.1 wt% to 5 wt% based on the total amount of the photosensitive resin composition for a light-shielding layer, and specifically 1 wt% to 3 wt%. When the photopolymerization initiator is contained within the above range, photopolymerization occurs sufficiently during exposure in a pattern formation process for producing a light shielding layer, which results in excellent sensitivity and improved transmittance.

(E) Solvent

The solvent is not particularly limited, but specific examples thereof include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methylhydroxyacetate, ethylhydroxyacetate and butylhydroxyacetate; Alkoxyalkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate and methyl 2-hydroxy-3-methyl butanoate; Or ethyl pyruvate. Examples of the ketone acid esters include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, Ethyl, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. These may be used alone or in combination of two or more.

In view of the miscibility and reactivity of the solvent, glycol ethers such as ethylene glycol monoethyl ether and the like; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycol such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be included as the balance relative to the total amount of the photosensitive resin composition for the light-shielding layer, and specifically 20% by weight to 90% by weight. When the solvent is contained within the above range, the photosensitive resin composition is excellent in coating property and excellent flatness can be maintained in a film having a thickness of 3 m or more.

(F) Other additives

The above-mentioned photosensitive resin composition may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid, in order to prevent stains and spots upon application, to prevent leveling, 3-amino-1,2-propanediol; A silane-based coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; And other additives such as a radical polymerization initiator.

Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These may be used singly or in combination of two or more.

Examples of the fluorine-based surfactant, BM Chemie BM-1000 ^® of社(four), BM-1100 ^®, and the like; Mecha Pack F 142D ^® , Copper F 172 ^® , Copper F 173 ^® , Copper F 183 ^® and the like manufactured by Dainippon Ink & Chemicals Incorporated; M. Sumitomo Co. Pro rod FC-135 ^® of社(g), the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass (Note)社(G) Saffron S-112 ^®, the same S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^® and the like; Toray silicone (Note) ^® SH-28PA of社(g), copper ^® -190, may be a commercially available product such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The additive can be easily adjusted according to desired properties.

Another embodiment provides a light-shielding layer produced using the above-described photosensitive resin composition for a light-shielding layer. The method of manufacturing the light-shielding layer is as follows.

(1) Coating and Film Formation Step

The photosensitive resin composition for a light-shielding layer described above is applied onto a substrate to which a predetermined pretreatment is applied by a spin or slit coating method, a roll coating method, a screen printing method, an applicator method or the like to a desired thickness, And then the solvent is removed by heating at a temperature of 70 to 90 DEG C for 1 to 10 minutes to form a coating film.

(2) Exposure step

In order to form a pattern necessary for the obtained coating film, a mask of a predetermined type is interposed therebetween and then an active line of 200 to 500 nm is irradiated.

As the light source used for the irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, and the like can be used.

Exposure dose at the light-shielding layer type photosensitive resin composition of each component, depending on the amount and the dry film thickness of, for example, using a high-pressure mercury lamp 500 mJ / cm ² (By a 365 nm sensor).

(3) Development step

Following the above exposure step, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution as a developing solution, so that only the exposed portion is left to form an image pattern.

(4) Post-treatment step

The image pattern obtained by the above-described development can be cured by heating again or by active ray irradiation or the like in order to obtain a pattern excellent in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength and storage stability.

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

( Shading layer  Preparation of Photosensitive Resin Composition)

The specifications of the components used in the production of the photosensitive resin composition for the light-shielding layer are as follows.

(A) Colorant

(A-1) Blue system  material

(A-1-1) A dye represented by the following formula (4) (cyan-1 of Kyowa Ink) was used.

[Chemical Formula 4]

(A-1-2) A mill base (Sakata Co.) containing a V23 pigment of BASF Co. was used.

(A-1-3) A mill base (Sakata Co.) containing a pigment of B15: 6 represented by the following formula (18) was used.

[Chemical Formula 18]

(A-2) Red  material

Orange 63 from Sakata Co., Ltd. was used.

(B) binder resin

As a cadmium binder resin, V259ME from NSCC was used.

(C) Photopolymerization  Monomer

Dipentaerythritol hexaacrylate was used.

(D) Light curing Initiator

IGR 369 from Ciba-Geigy Co. was used.

(E) Solvent

Propylene glycol methyl ether acetate was used.

(F) Additive

γ-glycidoxypropyltrimethoxysilane (S-710 from Chisso) was used.

Example  1 and 2 and Comparative Example  One

Each component was mixed with the composition shown in Table 1 below to prepare a photosensitive resin composition for a light-shielding layer. Specifically, after a photopolymerization initiator was dissolved in a solvent, the mixture was stirred for 30 minutes, and then a binder resin and a photopolymerizable monomer were added thereto, followed by stirring for 1 hour. The additive was added thereto, the colorant was finally added, and the mixture was stirred for 2 hours or more to prepare a photosensitive resin composition for a light-shielding layer.

(Unit: wt%) Example 1 Example 2 Comparative Example 1 (A) Colorant (A-1) Blue-based material (A-1-1) 3.85 4.71 - (A-1-2) 3.85 2.99 2.99 (A-1-3) - - 4.71 (A-2) Red-based material 0.86 0.86 0.86 (B) binder resin 2.56 2.56 2.56 (C) a photopolymerizable monomer 1.10 1.10 1.10 (D) a photopolymerization initiator 0.69 0.69 0.69 (E) Solvent 86.80 86.80 86.80 (F) Additive 0.29 0.29 0.29

Evaluation 1: Elution property  Measure

The photosensitive resin composition for a light-shielding layer prepared in Example 1 and Example 2 and Comparative Example 1 was applied on a predetermined pretreated substrate to a thickness of 2.0 탆 and then heated at 90 캜 for 4 minutes to remove the solvent, . Subsequently, the photomask was placed on the coated film and the entire surface was exposed at 40 mJ. Then, the coated film was baked at 220 ° C for 25 minutes using convection oven. Then, the coating film sample was placed in 4 mL of N-methylpyrrolidone at 100 DEG C and eluted for 10 minutes. Next, 0.2 g of the coating film sample was put into 30-fold diluted N-methylpyrrolidone using ICP-MS and the elution amount of Cu ions was measured. The results are shown in Table 2 below.

Evaluation 2: liquid crystal Reaction value  Measure

The photosensitive resin composition for a light-shielding layer prepared in Example 1 and Example 2 and Comparative Example 1 was coated on a glass substrate to form a coating film. A sample of the formed coating film was put into a liquid crystal and aged at a temperature of 80 캜 for 2 hours. This liquid crystal was injected between two electrodes and a voltage was applied to fabricate one sample device. Liquid crystal contamination was evaluated by measuring the liquid crystal reaction value using the autronic VHRM. The results are shown in Table 2 below. 　

Evaluation 3: Measurement of VHR value

The photosensitive resin composition for a light-shielding layer prepared in Example 1, Example 2 and Comparative Example 1 was coated on a glass substrate patterned with ITO to form a coating film. The formed coating film and the patterned ITO electrode were assembled with each other, pressed, injected with liquid crystal therebetween, and sealed to fabricate a sample device. The VHR values of these sample devices were measured using an autronic VHRM, and the results are shown in Table 2 below.

Elution amount of Cu ion (pg / cm ² ) Liquid crystal reaction value (%) VHR Value (%) Example 1 0.0 95 97 Example 2 0.0 95 97 Comparative Example 1 5625.2 75 82

As shown in Table 2 above, in the case of Examples 1 and 2 in which a blue-based material and a red-based material according to one embodiment were mixed as a coloring agent, compared with the case of Comparative Example 1 using a blue- Thus, it can be seen that the metal ions are not eluted at all and the liquid crystal defect is prevented and the light shielding property is excellent.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (11)

(A) a colorant comprising a blue-based material and a red-based material including a dye represented by the following formula (1);
(B) a binder resin;
(C) a photopolymerizable monomer;
(D) a photopolymerization initiator; And
(E) Solvent
Lt; / RTI >
Wherein the blue-based material does not contain a metal ion.
[Chemical Formula 1]

(In the formula 1,
X ¹ and X ² are each independently a carbon atom, a sulfur atom or an oxygen atom,
R ¹ to R ⁶ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 A substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 hetero A substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,
The Y ¹ ring group and the Y ² ring group are each independently a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, A substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group, RTI ID = 0.0 > C2-C30 < / RTI > heteroaryl group,
A ¹ is a halogen anion, a perhalogen acid anion, a haloacetate anion, an alkyl sulfate anion, a sulfonate anion or a hexafluorophosphate anion (PF ₆ ^- ),
and n ¹ to n ⁴ are each 0 or 1.)
The method according to claim 1,
The dye represented by Formula 1 is a dye represented by Formula 2 below.
(2)

(In the formula (2)
R ⁷ to R ¹² each independently represent a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 A substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 hetero A substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,
A ² is a halogen anion, a perhalogenated anion, a haloacetate anion, an alkylsulfate anion, a sulfonate anion or a hexafluorophosphate anion (PF ₆ ^- ).
The method according to claim 1,
Wherein the blue-based material further comprises a violet pigment.
The method according to claim 1,
The red-based material includes a dye, a pigment, or a combination thereof.
The method according to claim 1,
Wherein the red material is at least one selected from the group consisting of a perylene pigment, an anthraquinone pigment, a giant lake quinone pigment, an azo pigment, a diazo pigment, a quinacridone pigment, an anthracene pigment, Wherein the photosensitive resin composition is a photosensitive resin composition for a light-shielding layer.
The method according to claim 1,
Wherein the colorant comprises the blue-based material and the red-based material in a weight ratio of 10:90 to 90:10.
delete delete delete The method according to claim 1,
The light-sensitive resin composition for a light-
1% to 80% by weight of (A) the colorant;
0.1 to 30% by weight of the binder resin (B);
0.1 to 30% by weight of the (C) photopolymerizable monomer;
0.1 to 5% by weight of the photopolymerization initiator (D); And
The amount of the solvent (E)
A photosensitive resin composition for a light-shielding layer.
A light-shielding layer produced by using the photosensitive resin composition for a light-shielding layer according to any one of claims 1 to 6 and 10.