KR101432604B1 - Black photosensitive resin composition and light blocking layer using the same - Google Patents

Abstract

(A) a photopolymerization initiator comprising a first oxime compound having a different absorbance and a second oxime compound at a weight ratio of 1: 4 to 4: 1, (B) an organic binder resin, (C) ) Reactive unsaturated compound, and (E) a solvent, and a light-shielding layer made using the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black photosensitive resin composition and a light-

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

The black photosensitive resin composition is an indispensable material for the production of display elements such as color filters, liquid crystal display materials, organic light emitting devices (EL) and display panel materials. For example, a color filter such as a color liquid crystal display requires a light-shielding layer at a boundary portion between coloring layers such as red, green, and blue in order to enhance display contrast and coloring effect, The light-shielding layer is mainly formed of a black photosensitive resin composition.

As the market for smart phones and tablet PCs is rapidly growing, high-resolution displays are gaining popularity. Therefore, in order to realize high resolution, the number of pixels has to be increased to a level higher than the current level, and as the number of pixels increases, the line width of the black matrix should also be reduced to less than 10 μm.

However, it is difficult to realize a line width of 10um or less, and the film thickness decreases as the line width decreases. A half tone mask, a slit mask, and the like are required in the process in order to reduce the decrease in film thickness at a line width of 10um or less.

It is preferable that the black matrix is made of a material which does not decrease the film thickness even in fine lines because the intensity of the light passing through the halftone mask or the slit mask is higher than the intensity of light passing through the normal glass. Since the difference in the film thickness may vary depending on the exposure amount and the kind and ratio of the initiator, it is necessary that the material of the black matrix is developed in the direction of ensuring the process margin.

An embodiment of the present invention can improve the process margin by making it possible to realize a fine pattern of 10um or less without decreasing the film thickness by adjusting the tilt angle (gamma) of the film step to the exposure amount at an appropriate level while maintaining the sensitivity at an appropriate level. To provide a black photosensitive resin composition.

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

(A) a photopolymerization initiator comprising a first oxime compound having a different absorbance and a second oxime compound in a weight ratio of 1: 4 to 4: 1; (B) an organic binder resin; (C) a black pigment; (D) a reactive unsaturated compound; And (E) a solvent.

The photopolymerization initiator may include the first oxime compound and the second oxime compound at a weight ratio of 1: 3 to 3: 1.

The absorbance of the first oxime compound may be 325 nm or more and less than 335 nm, and the absorbance of the second oxime compound may be 335 nm or more and less than 345 nm.

The molecular weight of the first oxime compound may be 430 to 450 g / mol, and the molecular weight of the second oxime compound may be 400 to 420 g / mol.

The first oxime compound may include 1- (o-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H- The second oxime based compound may include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione.

The photopolymerization initiator (A) may further include one selected from an acetophenone-based compound, a benzophenone-based compound, and a combination thereof.

The black photosensitive resin composition comprises (A) 0.1 to 10% by weight of the photopolymerization initiator; (B) 0.5 to 20% by weight of the organic binder resin; (C) 1 to 40% by weight of the black pigment; (D) 1 to 20% by weight of the reactive unsaturated compound; And (E) the solvent balance.

The organic binder resin (B) may include one selected from a cardade resin, an acrylic resin, a polyimide resin, a polyurethane resin, and a combination thereof.

The black pigment (C) may include one selected from carbon black, black oil / inorganic pigment, and combinations thereof.

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

The light-shielding layer may include a pattern obtained by exposing the coating film through a mask and developing the mask, and the mask may include a half tone mask or a slit mask.

The inclination angle gamma of the film step with respect to the exposure amount of the light shielding layer may be 60 degrees or more.

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

By using the black photosensitive resin composition, it is possible to realize a fine pattern of 10um or less without reducing the film thickness while maintaining the sensitivity at an appropriate level, thereby realizing a light-shielding layer with improved process margin.

FIG. 1A is a conceptual view showing a method of obtaining a pattern of a light-shielding layer according to one embodiment, and FIG. 1B is a conceptual diagram showing a definition of a film step property of a light-shielding layer according to an embodiment.
FIG. 2 is a schematic view showing an example of a mask used for pattern formation in manufacturing a light-shielding layer according to an embodiment.
FIG. 3 is a schematic view showing another form of a mask used for pattern formation in manufacturing a light-shielding layer according to an embodiment.

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 C1- 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 imino group, an azido group, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, a carbamoyl group, A C 1 to C 20 alkyl group, a C 2 to C 20 alkenyl group, a C 2 to C 20 alkynyl group, a C 6 to C 30 aryl group, a C 3 to C 20 cycloalkyl group, a C 3 to C 20 cycloalkenyl group, Substituted with a substituent of a C2 to C20 heterocycloalkyl 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 black photosensitive resin composition according to one embodiment may include a photopolymerization initiator, an organic binder resin, a black pigment, a reactive unsaturated compound, and a solvent. The respective components will be described in detail below.

(A) Light curing Initiator

The photopolymerization initiator may be used by mixing different types of oxime compounds, and concretely, two kinds of oxime compounds having different absorbances may be mixed and used.

The absorbance of the first oxime compound may be specifically from 325 nm to less than 335 nm. The absorbance of the second oxime compound may be 335 nm or more and less than 345 nm.

The molecular weight of the first oxime compound is 430 to 450 g / mol, and the molecular weight of the second oxime compound is 400 to 420 g / mol.

Examples of the first oxime compound include 1- (o-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- have.

Examples of the second oxime compound include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and the like.

The photopolymerization initiator can be used by mixing the first oxime compound and the second oxime compound in a weight ratio of 1: 4 to 4: 1, and more specifically, in a weight ratio of 1: 3 to 3: 1 . In the case of mixing within the above-mentioned content ratio range, since the tilt angle (?) Of the film step with respect to the exposure amount in manufacturing the light-shielding layer is a large value in a predetermined range, The process margin can be sufficiently secured.

A half tone mask, a slit mask, and the like are required in the process in order to reduce the film thickness reduction while realizing a fine pattern of 10um or less.

It is preferable that the black matrix is made of a material which does not decrease the film thickness even in fine lines because the intensity of the light passing through the halftone mask or the slit mask is higher than the intensity of light passing through the normal glass. Since the difference in the film thickness may vary depending on the exposure amount and the kind and ratio of the initiator, it is necessary that the material of the black matrix is developed in the direction of ensuring the process margin.

A pattern can be formed by exposing the prepared coating film to an active ray after interposing the mask thereon and exposing the unnecessary portion. After the developing step, a difference in film thickness between the exposed portion and a portion exposed to less exposure due to the mask appears, and the difference in film thickness is also referred to as a film step.

FIG. 1A is a conceptual view showing a method of obtaining a pattern of a light-shielding layer according to one embodiment, and FIG. 1B is a conceptual diagram showing a definition of a film step property of a light-shielding layer according to an embodiment.

Referring to FIG. 1A, for example, a half tone mask having a characteristic that the intensity of light is increased higher than that of the conventional masks 1 to 3 is exposed to a coating film, . The difference in film thickness occurring at this time can be defined as a film step difference.

That is, in the case of a conventional conventional mask, intensity of light received by a coating film when light passes through a mask pattern of a small size is reduced. On the other hand, when a halftone mask is used, unexposed areas are exposed to about 10% It is possible to realize thin lines by increasing the intensity of light even in a mask pattern of a size.

Referring to FIG. 1B, the larger the tilt angle? Of the film step relative to the exposure amount, the greater the margin for the film thickness difference for realizing the fine pattern. That is, in order to secure a high process margin in realizing a fine pattern without reducing the film thickness, a good film step property is required, and the film step property is set such that the value of the tilt angle [gamma] As shown in FIG.

According to the definition above, when two kinds of oxime compounds having different absorbances are mixed in a specific ratio range, the inclination angle? Of the film step with respect to the exposure amount becomes a larger value than the predetermined range, It is possible to realize a fine pattern of 10um or less without decreasing the film thickness, thereby ensuring a sufficient process margin.

The photopolymerization initiator may be a mixture of one selected from the group consisting of an acetophenone compound, a benzophenone compound, and a combination thereof.

The acetophenone compound may be at least one compound selected from the group consisting of 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 2,2'-dichloroacetophenone, Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and combinations thereof.

The benzophenone compound may be at least one selected from the group consisting of benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, (Diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and combinations thereof. .

The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy .

The photopolymerization initiator may be contained in an amount of 0.1 to 10% by weight based on the total amount of the black photosensitive resin composition, and may be contained in an amount of 1 to 5% by weight. When the photopolymerization initiator is contained within the above range, the sensitivity of the radical is good, the color density of the black photosensitive resin composition solution is appropriately maintained, and the decrease of the transmittance due to the unreacted initiator can be prevented.

(B) Organic binder resin

As the organic binder resin, one selected from a cardade resin, an acrylic resin, a polyimide resin, a polyurethane resin, and a combination thereof can be used, and among them, a cardade resin can be used. When the cadene resin is used, the heat resistance, chemical resistance and adhesion of the black photosensitive resin composition can be improved.

In addition, the cado resin and the acrylic resin may be used in combination, or the cado resin may be used in a larger amount than the acrylic resin.

The cation resin may be a compound containing a repeating unit represented by the following formula (1).

[Chemical Formula 1]

(In the formula 1,

R ₂₄ To R < ₂₇ > are the same or different and each represents 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 acrylic group or a methacryl group)

R ₃₀ are the same or different and each represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, an acrylic group or a methacrylic group,

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 from each other, A substituted or unsubstituted C1 to C20 alkyl group), or a compound represented by the following general formulas (2) to (12)

Z ₂ are the same or different from each other, and the acid dianhydride residue.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(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.

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

The cation resin can be specifically obtained by reacting a compound represented by the following formula (13) with a tetracarboxylic acid dianhydride.

[Chemical Formula 13]

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 weight average molecular weight of the cardedo resin may be 1,000 to 20,000 g / mol, and specifically 3,000 to 10,000 g / mol. When the weight average molecular weight of the cadene resin is within the above range, excellent patterning property and developability can be obtained in the production of the light-shielding layer.

The acrylic 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 to 50% by weight, specifically 10 to 40% by weight based on the total amount of the acrylic resin.

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 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 weight average molecular weight of the acrylic resin may be 3,000 to 150,000 g / mol, specifically 5,000 to 50,000 g / mol, and more specifically 2,000 to 30,000 g / mol. 　　 When the weight average molecular weight of the acrylic resin is within the above range, the black photosensitive resin composition 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 resin may be 15 to 60 mgKOH / g, and specifically 20 to 50 mgKOH / g. When the acid value of the acrylic resin is within the above range, the resolution of the pixel pattern is excellent.

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

The organic binder resin preferably has a ratio of the total amount of the black photosensitive resin composition 　 0.5 to 20% by weight, and more specifically, 　 1 to 10% by weight. When the organic 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 in the production of the light-shielding layer.

(C) Black pigment

The black pigment may be one selected from carbon black, black oil / inorganic pigment, and combinations thereof.

The kind of the carbon black is not particularly limited, and examples thereof include graphitized carbon, furnace black, acetylene black, and ketjen black.

As the black organic / inorganic pigment, a mixture of two or more kinds of pigments for realizing a color resist can be used, and black such as titanium (TiO _x ) black, perylene black, aniline black pigment, All available organic / inorganic pigments can be used.

The black ink / inorganic pigment may be contained in an amount of 5 to 60% by weight, specifically 30 to 60% by weight based on the total solid content of the black photosensitive resin composition. When it is included within the above range, the light shielding property is excellent, and there is no fear of light leakage, and an excellent pattern can be realized.

The black pigment may be used in the form of a pigment dispersion prepared by mixing together with a dispersant, a solvent and the like.

A first pigment dispersion prepared by mixing the black organic / inorganic pigment with a dispersant, a solvent and the like; and a second pigment dispersion prepared by mixing the carbon black with a dispersant, a solvent and the like are mixed with each other, and then the black photosensitive resin It may also be used in the composition. Alternatively, a pigment dispersion prepared by simultaneously mixing the black / organic pigment and the carbon black with a dispersant, a solvent and the like may be used in the black photosensitive resin composition.

The dispersant may help the black pigment to be uniformly dispersed in the solvent.

Examples of the dispersing agent include nonionic compounds, anionic compounds, cationic compounds and the like. Specific examples thereof include polyalkylene glycols and 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, and alkylamines.

DISPERBYK-161, DISPERBYK-160, DISPERBYK-161, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-160 and DISPERBYK-160 of BYK Co., -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 and the like; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400 and EFKA-450 of EFKA Chemical Co., Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000 from Zeneka; Or PB711 and PB821 from Ajinomoto.

The dispersant may be contained in an amount of 0.1 to 15% by weight based on the total weight of the black photosensitive resin composition. When the dispersant is contained within the above range, the black photosensitive resin composition is excellent in dispersibility, and therefore, it is excellent in stability, developability and patterning property in the production of the light-shielding layer.

The solvent is as described below.

The black pigment may be contained in an amount of 1 to 40% by weight based on the total amount of the black photosensitive resin composition, specifically 5 to 30% by weight. When the black pigment is contained within the above range, the light-shielding layer is excellent in insulation, high optical density, and excellent developability and processability. 　

(D) a reactive unsaturated compound

The reactive unsaturated compound may be monomers or oligomers generally used in a black photosensitive resin composition, and monofunctional or polyfunctional esters of (meth) acrylic acid having at least one ethylenically unsaturated double bond may be used.

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

Examples of commercially available products of the above reactive unsaturated compounds are as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®; KAYARAD TC-110S ^® and TC-120S ^{® from} Nihon Kayaku Co., Ltd.; Osaka yukki the like Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^®; KAYARAD HDDA ^® , HX-220 ^® and R-604 ^{® from} Nihon Kayaku Corporation; Osaka yukki the like Kagaku Kogyo Co., Ltd. of ^{社V-260 ®, V-} 312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -7100 ^® , copper M-8030 ^® , copper M-8060 ^® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. These products may be used alone or in combination of two or more.

The reactive unsaturated compound may be contained in an amount of 1 to 20% by weight based on the total amount of the black photosensitive resin composition, specifically, 1 to 15% by weight. When the above-mentioned reactive unsaturated compound is contained within the above range, compatibility with the organic binder resin is improved, and patterning property in the production of the light shielding layer and sensitivity in the presence of oxygen are excellent, and a smooth surface film can be obtained.

(E) Solvent

The solvent may be a material that has compatibility with the photopolymerization initiator, the organic binder resin, the black pigment, and the reactive unsaturated compound but does not react.

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 Benzyl alcohol, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, Ethyl benzoate, 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 in an amount of 50 to 70% by weight based on the total amount of the black photosensitive resin composition. When the solvent is contained within the above range, the black photosensitive resin composition has an appropriate viscosity, so that the processability of the light-shielding layer is excellent.

(F) Other additives

The black photosensitive resin composition may further include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group in order to improve adhesion with a substrate.

Specific 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.

The silane coupling agent may be used 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 comprise a surfactant for improving coatability and preventing defect formation, if necessary.

Examples of the surfactants include, BM Chemie Corporation ^{BM-1000 ®, 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., Inc. Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Inc. Saffron S-112 ^®, the same S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; ^® Toray Silicone Co., Ltd.'s SH-28PA, copper -190 ^®, may be used a fluorine-containing surfactants commercially available under the name such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The surfactant may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the organic binder resin. When the surfactant is contained within the above range, coating uniformity is ensured, no staining occurs, and wetting of the glass substrate is excellent.

The black photosensitive resin composition may contain a certain amount of other additives such as an antioxidant and a stabilizer within a range that does not impair the physical properties.

Another embodiment provides a light-shielding layer made using the above-mentioned black photosensitive resin composition. The method of manufacturing the light-shielding layer is as follows.

(1) Coating and Film Formation Step

The above-mentioned black photosensitive resin composition is applied onto a predetermined pretreated substrate by a method such as spin or slit coat method, roll coating method, screen printing method or applicator method to a desired thickness, for example, a thickness of 0.9 to 4.0 탆 After coating, 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.

The coating film has a value of 4.0 or more at an optical density of 1.0 m, and the larger the optical density, the better. When the optical density is in the above range, there is no possibility that the lower light leaks out.

(2) Exposure step

After forming a mask of a predetermined type in order to form a pattern necessary for the obtained coating film, an active line of 200 to 500 nm is irradiated.

The mask can be used in various forms, specifically, in the form shown in FIG. 2 or FIG.

FIG. 2 is a schematic view showing one embodiment of a mask used for pattern formation in the production of a light-shielding layer according to an embodiment, FIG. 3 is a schematic view showing a mask used for forming a pattern in a light- Fig.

FIG. 2 shows a mask with a 100% shielded area, and FIG. 3 shows a mask with a 100% transparent area and a 10 to 90% transparent area together. In FIG. 3, a region that is 10 to 90% transmissive may have a half tone or a slit shape.

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.

The exposure dose varies depending on the kind of each component of the above-mentioned black photosensitive resin composition, the blending amount, and the dried film thickness. For example, when a high-pressure mercury lamp is used, the exposure dose is 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.

The light-shielding layer prepared using the black photosensitive resin composition in which two kinds of oxime compounds having different absorbances as photopolymerization initiators were mixed at a weight ratio of 1: 4 to 4: 1 was used as the light- May be greater than or equal to 60 degrees, more specifically greater than or equal to 65 degrees, and more specifically, greater than or equal to 70 degrees. When the inclination angle gamma of the film step relative to the exposure amount is within the above range, a fine pattern of 10um or less can be realized without decreasing the film thickness with a high process margin.

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.

Example  1 to 5 and Comparative Example  1 to 7

A black photosensitive resin composition according to each of Examples 1 to 5 and Comparative Examples 1 to 7 was prepared with the compositions shown in the following Table 1 by using the following components.

(A) Light curing Initiator

OXE01 (absorbance: 330 nm, molecular weight: 445.6 g / mol) of Ciba-Geigy Corporation (A-1) oxime compound was used.

OXE02 (absorbance: 340 nm, molecular weight: 412.5 g / mol) of Ciba-Geigy Co., Ltd. (A-2) oxime compound was used.

(A-3) Triazine-based compound STR2BP from Respe was used.

(B) Organic binder resin

159 g of 3,3-bis (4-hydroxyphenyl) -2-benzofuran-1-one, 426.6 g of epichlorohydrin and 160 g of a 50% alkali aqueous solution were mixed in a 1 L flask, and reacted at 95 DEG C for 1 hour To obtain bisphenylbenzofuran type epoxy resin. 215 g of the obtained bisphenylbenzofuran type epoxy resin, 450 mg of triethylbenzylammonium chloride, 100 mg of 2,6-diisobutylphenol, and 72 g of acrylic acid were mixed, and air was blown at a rate of 25 ml per minute, To complete dissolution. Thereafter, the mixture was cooled to room temperature to obtain a colorless transparent solid bisphenylbenzofuran type epoxy acrylate. 287 g of the synthesized biphenylbenzofuran type epoxy acrylate was dissolved in 2 kg of cellosolve acetate to prepare a solution. Then, 38 g of 1,2,3,6-tetrahydrophthalic anhydride and 80 g of benzophenone tetracarboxylic acid dianhydride 80.5 g and 1 g of tetraethylammonium bromide were added and slowly heated to react at 110 to 115 ° C for 2 hours to obtain a cadocene resin having a weight average molecular weight of 5,000 g / mol.

(C) a black pigment dispersion

(C-1) A pigment dispersion (MICHONY Corporation, TCZ-121) containing a pigment of red, blue and violet as a main component was used.

(C-2) pigment dispersion (Sakata Co., Cl-M-050) containing carbon black was used.

(D) a reactive unsaturated compound

Dipentaerythritol hexaacrylate was used.

(E) Solvent

Propylene glycol methyl ether acetate was used.

(F) Other additives

As the silane coupling agent,? -Glycidoxypropyltrimethoxysilane (S-510 of Chisso) was used.

Example Comparative Example One 2 3 4 5 One 2 3 4 5 6 7 (A)
Photopolymerization initiator
(A-1) 0.10 0.13 0.25 0.37 0.40 0.5 - - 0.07 0.43 0.1 - (A-2) 0.40 0.37 0.25 0.13 0.10 - 0.5 - 0.43 0.07 - 0.1 (A-3) - - - - - - - 0.5 - - 0.4 0.4 (B) Organic
Binder resin 2 2 2 2 2 2 2 2 2 2 2 2 (C) a black pigment dispersion (C-1) 40 40 40 40 40 40 40 40 40 40 40 40 (C-2) 5 5 5 5 5 5 5 5 5 5 5 5 (D) a reactive unsaturated compound One One One One One One One One One One One One (E) Solvent 51.495 51.495 51.495 51.495 51.495 51.495 51.495 51.495 51.495 51.495 51.495 51.495 (F) Additive 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005

Rating 1: Pattern Formability  And Developability  Measure

Each of the coating films according to Examples 1 to 5 and Comparative Examples 1 to 7 obtained above was irradiated with light having a wavelength of 365 nm at a dose of 40 mJ / cm ² using a mask as shown in Fig. Developed in an aqueous solution diluted with 1% by weight of potassium hydroxide at 23 DEG C for 1 minute, then rinsed with pure water for 1 minute. The pattern obtained by this method was cured by heating in an oven at 220 캜 for 30 minutes, and then the shape of the pattern was visually observed using an optical microscope. The results are shown in Table 2 below.

<Evaluation Criteria>

?: Good formation and developing property of 10 占 퐉 pattern

DELTA: Formability and developing property of a 10 mu m pattern were poor

×: No formation of 10 μm pattern

Evaluation 2: Film step  Characteristic (γ) measurement

Each of the patterns according to Examples 1 to 5 and Comparative Examples 1 to 7 obtained above was observed with an optical microscope by using a device of P-16 (profiler) of KLA under the condition that the tilt angle And the results are shown in Table 2 below.

Pattern forming property Developability γ (°) Example 1 ○ ○ 73 Example 2 ○ ○ 72 Example 3 ○ ○ 68 Example 4 ○ ○ 63 Example 5 ○ ○ 62 Comparative Example 1 × ○ 22 Comparative Example 2 ○ ○ 52 Comparative Example 3 △ ○ 48 Comparative Example 4 ○ ○ 57 Comparative Example 5 △ ○ 28 Comparative Example 6 × × 22 Comparative Example 7 △ ○ 23

The black photosensitive resin compositions of Examples 1 to 5, which were prepared by mixing two kinds of oxime compounds having different absorbances at a weight ratio of 1: 4 to 4: 1 through the above Table 2, It can be understood that a fine pattern can be realized without decreasing the film thickness while maintaining the sensitivity at an appropriate level.

Specifically, in the case of Comparative Examples 1 to 3, 6 and 7 in which two kinds of oxime compounds having different absorbances were not used, there was a difference in pattern formation and developability depending on the kind of the initiator, Respectively.

In the case of Comparative Examples 4 and 5 in which two kinds of oxime compounds having different absorbances were mixed in a specific ratio range, the gamma value to be achieved in the present invention was not reached.

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 (12)

(A) a photopolymerization initiator comprising a first oxime compound having a different absorbance and a second oxime compound at a weight ratio of 1: 4 to 2: 3;
(B) an organic binder resin;
(C) a black pigment;
(D) a reactive unsaturated compound; And
(E) Solvent
Lt; / RTI &gt;
The molecular weight of the first oxime compound is 430 to 450 g / mol,
And the molecular weight of the second oxime compound is 400 to 420 g / mol.
The method according to claim 1,
Wherein the photopolymerization initiator comprises the first oxime compound and the second oxime compound in a weight ratio of 1: 3 to 2: 3.
The method according to claim 1,
The absorbance of the first oxime compound is 325 nm or more and less than 335 nm,
And the absorbance of the second oxime compound is not less than 335 nm and less than 345 nm.
delete The method according to claim 1,
Wherein the first oxime compound comprises 1- (o-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-
Wherein the second oxime compound comprises 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione.
The method according to claim 1,
The photopolymerization initiator (A) further comprises one selected from an acetophenone-based compound, a benzophenone-based compound, and a combination thereof.
The method according to claim 1,
The black photosensitive resin composition
(A) 0.1 to 10% by weight of the photopolymerization initiator;
(B) 0.5 to 20% by weight of the organic binder resin;
(C) 1 to 40% by weight of the black pigment;
(D) 1 to 20% by weight of the reactive unsaturated compound; And
(E) the solvent remaining amount
Wherein the black photosensitive resin composition comprises:
The method according to claim 1,
Wherein the organic binder resin (B) comprises one selected from the group consisting of carnaic resin, acrylic resin, polyimide resin, polyurethane resin, and combinations thereof.
The method according to claim 1,
The black pigment (C) comprises one selected from carbon black, black oil / inorganic pigment, and combinations thereof.
A light-shielding layer produced by using the black photosensitive resin composition of any one of claims 1 to 3 and 5 to 9.
11. The method of claim 10,
Wherein the light-shielding layer includes a pattern obtained by exposing a coating film through a mask, and then developing the coating film,
Wherein the mask comprises a half tone mask or a slit mask.
11. The method of claim 10,
Wherein a tilt angle (gamma) of a film step relative to an exposure amount of the light shielding layer is 60 DEG or more.

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