WO2016076652A1 - Black matrix photoresist composition for liquid crystal display panel - Google Patents

Abstract

The present invention relates to a black material photoresist composition for a liquid crystal display panel, wherein the composition has no influence on the transmittance of the liquid crystal display panel due to the use of an excellent photopolymerization initiator, suppresses the reduction in the reflectance of a black matrix thin film and the inhibition of generation of color difference, and is advantageous in forming patterns due to favorable deep-section curing. Specifically, an oxime ester fluorene derivative compound used as a photopolymerization initiator in the present invention is represented by chemical formula 1 described in the specification.

Description

Black Matrix Photoresist Composition for Liquid Crystal Display Panels

The present invention relates to a black matrix, which is a light-sensitive photosensitive resin composition used for a liquid crystal display. More specifically, the present invention relates to a photosensitive resin composition that can be used to prepare black matrices used in liquid crystal displays using photolithography.

This application claims the priority based on Korean Patent Application No. 10-2014-0157328, filed November 12, 2014, all the contents disclosed in the specification of the application is incorporated in this application.

In addition, this application claims the priority based on Korea Patent Application No. 10-2015-0158807 filed on November 12, 2015, all the contents disclosed in the specification of the application is incorporated in this application.

In general, the black matrix photoresist composition is an essential material for the production of color filters included in display devices such as color filters, liquid crystal displays, organic electroluminescent devices, and display panels. The color filter of the liquid crystal display device is used to prevent the mixing of R (red), G (green), B (blue), or in the touch panel device may be used for the bezel to cover the X, Y metal electrodes.

In display liquid crystal display devices, low temperature poly-silicon (LTPS) and oxide thin film transistors have been actively studied as devices for use in high-resolution driving over UD (Ultra Definition) and high-speed driving of 240 Hz or more.

In general, since the oxide thin film transistor changes the properties of the semiconductor by light, the above-described problem is minimized by introducing a light blocking layer. Since the light shielding layer is mainly formed of a metal light shielding layer since a subsequent process such as PE-CVD is performed at a high temperature after the formation of the light shielding layer, the metal light shielding layer has high reflectivity and light is reflected between the source, the drain electrode, and the light shielding layer. There is a problem that the parasitic voltage is generated between the source and drain electrodes to act as an element that resists the operation of the device and increases the load of the data line.

In particular, in OLEDs and transparent displays, a light shielding layer may be introduced to eliminate a characteristic in which the contrast ratio is significantly lowered by reflection of upper and lower metal interconnections.

[Preceding technical literature]

[Patent Documents]

(Patent Document 1) [Patent Document 1] KR 2007-0131523 (2007.12.14)

(Patent Document 2) [Patent Document 2] KR 2009-0131415 (2009.12.28)

(Patent Document 3) [Patent Document 3] JP 2011-247437 (2011.11.11)

Accordingly, the problem to be solved by the present invention is to provide a black matrix photoresist composition for a liquid crystal display panel which suppresses the effect of reducing the reflectance and inhibits the occurrence of color difference, and is advantageous in the processability of the pattern formation and the development process because the deep curing is advantageous. The purpose is.

In order to achieve the above object, the present invention provides a black matrix photoresist composition using an oxime ester fluorene derivative compound represented by the following Chemical Formula 1 as a photopolymerization initiator.

[Formula 1]

In Chemical Formula 1,

R ₁ to R ₃ are each independently hydrogen, halogen, (C1-C20) alkyl, (C6-C20) aryl, (C1-C20) alkoxy, (C6-C20) aryl (C1-C20) alkyl, hydroxy ( C1-C20) alkyl, hydroxy (C1-C20) alkoxy (C1-C20) alkyl or (C3-C20) cycloalkyl;

A is hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C1-C20) alkoxy, (C6-C20) aryl (C1-C20) alkyl, hydroxy (C1-C20) alkyl, hydroxy ( C1-C20) alkoxy (C1-C20) alkyl, (C3-C20) cycloalkyl, amino, nitro, cyano or hydroxy;

n is 0 or 1;

Substituents including the "alkyl", "alkoxy" and other "alkyl" moieties described in the present invention include all linear or pulverized forms, and "cycloalkyl" includes not only a single ring system but also various ring hydrocarbons. "Aryl" described in the present invention is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and is a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms in each ring as appropriate. It includes a system, including a form in which a plurality of aryl is connected by a single bond. "Hydroxyalkyl" means OH-alkyl in which a hydroxy group is bonded to the alkyl group defined above, and "hydroxyalkoxyalkyl" means hydroxyalkyl- O -alkyl in which an alkoxy group is bonded to the hydroxyalkyl group.

In addition, the '(C1-C20) alkyl' group described in the present invention is preferably (C1-C10) alkyl, more preferably (C1-C6) alkyl. The '(C6-C20) aryl' group is preferably (C6-C18) aryl. The '(C1-C20) alkoxy' group is preferably (C1-C10) alkoxy, more preferably (C1-C4) alkoxy. The '(C6-C20) aryl (C1-C20) alkyl' group is preferably (C6-C18) aryl (C1-C10) alkyl, more preferably (C6-C18) aryl (C1-C6) alkyl. The 'hydroxy (C 1 -C 20) alkyl' group is preferably hydroxy (C 1 -C 10) alkyl, more preferably hydroxy (C 1 -C 6) alkyl. The 'hydroxy (C1-C20) alkoxy (C1-C20) alkyl' group is preferably hydroxy (C1-C10) alkoxy (C1-C10) alkyl, more preferably hydroxy (C1-C4) alkoxy (C1) -C6) alkyl. The '(C3-C20) cycloalkyl' group is preferably (C3-C10) cycloalkyl.

More specifically, R ₁ to R ₃ are each independently hydrogen, bromo, chloro, iodo, methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, t -butyl, n -pentyl , i -pentyl, n -hexyl, i -hexyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy, n -propyloxy, i -propyloxy, n -Butoxy, i -butoxy, t -butoxy, hydroxymethyl, hydroxyethyl, hydroxy n -propyl, hydroxy n -butyl, hydroxy i -butyl, hydroxy n -pentyl, hydroxy i- Pentyl, hydroxy n -hexyl, hydroxy i -hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, Hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl;

A is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, phenyl, naphthyl, biphenyl, terphenyl anthryl, indenyl, phenanthryl, methoxy, Ethoxy, propaneoxy, butoxy, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxy Hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, amino, nitro, cyano or hydroxy, but is not limited thereto.

As the oxime ester fluorene derivative compound according to the present invention, the following compounds are representatively mentioned, but the following compounds are not intended to limit the present invention.

In the present invention, the oxime ester fluorene derivative compound represented by Chemical Formula 1 is included in the black matrix photoresist composition as a photopolymerization initiator.

The black matrix photoresist composition of the present invention includes an oxime ester fluorene derivative compound represented by Chemical Formula 1, a binder resin, a polymerizable compound having an ethylenically unsaturated bond, a colorant, and the like, and a reduction in reflectance and inhibition of color difference generation. It is excellent in thin film properties, such as the point which suppresses a phenomenon and advantageously deep-hardens, and is advantageous for pattern formation.

In the black matrix photoresist composition of the present invention, an acrylic resin, a cardo resin, a silicone resin, or a mixed resin thereof, which is an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in the side chain, may be used as the binder resin.

The binder resin may control its content in order to provide pattern properties, thin film properties such as heat resistance and chemical resistance. For example, 3 to 50 wt% may be used based on 100 wt% of the photoresist composition. The binder resin preferably has a weight average molecular weight of 2,000 to 300,000, and a dispersion degree of 1.0 to 10.0, more preferably a weight average molecular weight of 4,000 to 100,000,00.

The acrylic polymer is a copolymer of monomers including the following monomers, and examples of such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and pentyl ( Meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (Meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate and hexadecyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, acrylic acid, Methacrylic acid, itaconic acid, maleic acid, maleic acid anhydride, maleic acid monoalkyl ester, monoalkyl itaconate, monoalkyl fumaleate, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (Meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-methyl oxetane-3-methyl (meth) acrylate, 3- Ethyl oxetane-3-methyl (meth) acrylate, styrene, α-methylstyrene, acetoxystyrene, N -methylmaleimide, N -ethylmaleimide, N -propylmaleimide, N -butylmaleimide, N − Cyclohexyl maleimide, (meth) acrylamide, N -methyl (meth) acrylamide, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.

The acrylic polymer having an acrylic unsaturated bond in the side chain is a copolymer obtained by adding an epoxy resin to an acrylic copolymer containing carboxylic acid, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and maleic acid monoalkyl ester. Acrylic monomer containing an acid, alkyl (meth) acrylates, such as methyl (meth) acrylate and hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl ( Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylates, styrene, α- methyl styrene, acetoxy-styrene, N - methyl maleimide, N - ethyl maleimide, N - propyl maleimide, N - butyl maleimide, N - cyclohexyl maleimide, ( L) acrylamide, N - methyl (meth) glycidyl acrylate in the copolymer containing a carboxylic acid obtained by copolymerizing monomers of two or more thereof, such as acrylamide, glycidyl acrylate, glycidyl methacrylate, 3,4- Obtained by addition reaction of epoxy resins, such as epoxy butyl (meth) acrylate, 2, 3- epoxy cyclohexyl (meth) acrylate, and 3, 4- epoxy cyclohexyl methyl (meth) acrylate, at the temperature of 40-180 degreeC Binder resin can be used.

Another example of an acrylic polymer having an acrylic unsaturated bond in the side chain is a copolymer in which a carboxylic acid is added to an acrylic copolymer containing an epoxy group, and glycidyl acrylate, glycidyl methacrylate, 3,4- Acrylic monomer and methyl (meth) acrylate containing epoxy groups, such as epoxy butyl (meth) acrylate, 2, 3- epoxycyclohexyl (meth) acrylate, and 3, 4- epoxycyclohexyl methyl (meth) acrylate, Alkyl (meth) acrylates, such as hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dish Clofenthenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, styrene, α-methylstyrene, acetoxy steel Monomers such as ene, N -methylmaleimide, N -ethylmaleimide, N -propylmaleimide, N -butylmaleimide, N -cyclohexyl maleimide, (meth) acrylamide and N -methyl (meth) acrylamide 40-180 degreeC with the acrylic monomer containing the carboxylic acid, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and monoalkyl ester, in the acrylic copolymer containing the epoxy group obtained by copolymerizing 2 or 2 or more types The binder resin obtained by addition reaction at the temperature of can be used.

In addition, according to an embodiment of the present invention, a cardo-based resin may be used as the binder resin, and the cardo-based resin refers to an acrylic binder resin including a fluorene group in a main chain, and is not particularly limited in structure.

In addition, siloxane resin may be used as the silicone resin, and more specifically, the siloxane resin disclosed in Korean Patent No. 10-1537771 may be used as the silicone resin, and a manufacturing method may also be prepared by the method described in the patent. Can be. The siloxane resin may have an acid value in the range of 10 to 200 mgKOH / g resin when titrating KOH.

The siloxane resin usable in one embodiment of the present invention may be a siloxane resin including a polymerized unit represented by the following Chemical Formula 2 and a polymerized unit represented by the following Chemical Formula 3.

[Formula 2]

XR ₄ -SiO _3/2

In Chemical Formula 2,

R ₄ is a linear or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylene group having 7 to 20 carbon atoms substituted with an aryl group, and an arylene group having 7 to 20 carbon atoms substituted with an alkyl group. Or a group having 7 to 20 carbon atoms, in which an alkylene group and an arylene group are connected.

X is hydroxy, carboxylic acid, carboxylic anhydride, carboxylic anhydride derivative, imide, imide derivative, amide, amide derivative, amine or mercanto,

[Formula 3]

R ₄ SiO _{(4-n) / 2}

In Chemical Formula 3,

Each R ₄ is independently hydrogen, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 10 carbon atoms, or an acyloxy group having 2 to 10 carbon atoms, A plurality of R ₂ in the molecule is the same or different from each other, n is an integer of 0 to 3, the polymer unit of n = 3 may be used in combination with another polymer unit other than n is 3.

The siloxane resin may be composed of 5 to 40 mol% of the polymerized units of Formula 1 and 95 to 60 mol% of the polymerized units of Formula 2 based on 100 mol% of the polymerized units of Formula 1 and the polymerized units of Formula 2.

As a specific example of the siloxane resin, a siloxane resin including the first polymer unit represented by the following Chemical Formulas 4 to 17 and the second polymer unit listed below may be used, but is not limited thereto.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

(In each of the above formula, m and n may be each independently an integer of 1 to 20.)

Further, as the monomer forming the second polymer unit, tetraalkoxy silane, trialkoxy silane, methyl trialkoxy silane, ethyl trialkoxy silane, n-propyl trialkoxy silane, isopropyl trialkoxy silane, n-butyl trialkoxy silane , tert-butyl trialkoxy silane, phenyl trialkoxy silane, naphtha trialkoxy silane, vinyl trialkoxy silane, methacryloxymethyl trialkoxy silane, 2-methacryloxyethyl trialkoxy silane, 3-methacryloxypropyl trialkoxy silane , 3-methacryloxypropyl methyl dialkoxy silane, 3-methacryloxypropyl ethyl dialkoxy silane, acryloxymethyl trialkoxy silane, 2-acryloxyethyl trialkoxy silane, 3-acryloxypropyl trialkoxy silane, 3- Acryloxypropyl methyl dialkoxy silane, 3-acryloxypropyl ethyl dialkoxy silane, 3-glycidyloxypropyl trialkoxy Cysilane, 2-epoxycyclohexylethyl trialkoxy silane, 3-epoxycyclohexylpropyl trialkoxy silane, dimethyl alkoxy silane, diethyl dialkoxy silane, dipropyl dialkoxy silane, diphenyl dialkoxy silane, diphenyl silanediol and One or more selected from the group consisting of phenylmethyl dialkoxysilanes can be used. Here, alkoxy is linear, branched or cyclic aliphatic or aromatic alkoxy having 1 to 7 carbon atoms, and may be a halogen compound capable of hydrolysis.

In the black matrix photoresist composition of the present invention, the polymerizable compound having an ethylenically unsaturated bond serves to form a pattern by crosslinking by photoreaction at the time of pattern formation and crosslinking at high temperature to impart chemical resistance and heat resistance. The polymerizable compound having an ethylenically unsaturated bond may be contained in an amount of 1 to 200 parts by weight, preferably 10 to 150 parts by weight, more preferably 50 to 120 parts by weight, based on 100 parts by weight of the binder resin. When the content of the polymerizable compound having an ethylenically unsaturated bond satisfies this range, the problem of excessively high degree of crosslinking can be prevented and ductility of an appropriate pattern can be maintained.

The polymerizable compound having an ethylenically unsaturated bond is specifically methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acryl Alkyl ester of (meth) acrylic acid, such as the rate, glycidyl (meth) acrylate, polyethyleneglycol mono (meth) acrylate whose number of ethylene oxide groups is 2-14, ethylene glycol di (meth) acrylate, ethylene oxide group Polyethylene glycol di (meth) acrylate having a number of from 2 to 14, propylene glycol di (meth) acrylate having a number of from 2 to 14 of propylene oxide group, trimethylolpropanedi (meth) acrylate, bisphenol A diglycidyl ether Acrylic acid adduct, phthalic acid diester of dihydroxy ethyl (meth) acrylate, toluene diisocy of dihydroxyethyl (meth) acrylate Nate adduct, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylic A compound obtained by esterifying a polyhydric alcohol and α, diunsaturated carboxylic acid, such as a latent, dipentaerythritol tri (meth) acrylate, an acrylic acid adduct of a polyhydric glycidyl compound, such as a trimethylolpropanetriglycidyl ether acrylic acid adduct. These can be mentioned, These can be used individually or in combination of 2 or more types, respectively.

In addition, the amount of the oxime ester fluorene derivative compound of Formula 1 included as a photopolymerization initiator in the black matrix photoresist composition of the present invention is a content for minimizing the reflectance of black matrix, suppressing color difference, and smoothing the deep curing It may be 0.01 to 50 parts by weight, preferably 0.02 to 25 parts by weight, 0.5 to 10 parts by weight based on 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond.

When the content of the photopolymerization initiator satisfies this range, the degree of photocuring is ensured, thereby making it easier to form a pattern due to the developability difference between the exposed portion and the non-exposed portion, and preventing the formation of a T-shaped pattern due to excessive upper curing. The desired pattern shape can be obtained.

According to one embodiment of the photoresist composition of the present invention, a thioxanthone compound, acetophenone compound, biimidazole compound, triazine compound, thiol compound as an additional photopolymerization initiator in addition to the oxime ester fluorene derivative compound of Chemical Formula 1 It may further comprise one or two or more selected from the group consisting of O-acyl oxime compounds other than the compound represented by the formula (1).

As said thioxanthone type compound, for example, thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- dichloro Thioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- diisopropyl thioxanthone, etc. can be used. As said acetophenone type compound, 2-methyl-1- [4- (methylthio) phenyl] -2- morpholino propane- 1-one, 2-benzyl-2- dimethylamino-1- ( 4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like can be used. As said biimidazole type compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl- 1,2'-biimidazole, 2,2, for example '-Bis (2,4-dichlororophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichloro Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like. Examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine and 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4 , 6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine , 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl)- 4,6-bis (trichloromethyl) -s-triazine and the like can be used.

As said O-acyl oxime type compound, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyl oxime), ethanone-1- [9-ethyl, for example] -6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydro Furanylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6-X2-methyl-4- (2,2-dimethyl- 1,3-dioxoranyl) methoxybenzoyl r-9H-carbazol-3-yl] -1- (O-acetyloxime) and the like can be used.

The additional photopolymerization initiator other than the oxime ester fluorene derivative compound of formula 1 used as the photopolymerization initiator in the photoresist composition of the present invention is 0.01 to 20 parts by weight, preferably 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond. 0.05 to 10 parts by weight may be used.

In addition, the black matrix photoresist composition of the present invention may further include a silicone-based compound having an epoxy group or an amine group as an adhesion aid as necessary. In the black matrix photoresist composition, the silicone-based compound may improve adhesion between the ITO electrode and the photoresist composition and may increase heat resistance after curing. Examples of the silicone compound having an epoxy group or an amine group include (3-glycidoxy propyl) trimethoxysilane, (3-glycidoxy propyl) triethoxysilane, and (3-glycidoxy propyl) methyldimethoxy silane. Phosphorus, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxy butyl Trimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrie Methoxysilane, aminopropyltrimethoxy silane, and the like, and these may be used alone or in combination of two or more thereof. The content of the silicon compound having the epoxy group or the amine group may be 0.0001 to 20 parts by weight based on 100 parts by weight of the binder resin.

In addition, the black matrix photoresist composition of the present invention may further include a compatible additive such as a photosensitizer, a thermal polymerization inhibitor, an antifoaming agent, a leveling agent and the like as necessary.

In addition, as the colorant of the present invention, at least one selected from carbon black, titanium black, acekylene black, aniline black, perylene black, strontium titanate, chromium oxide, and ceria, which preferably exhibits light blocking properties, may be used. . The content of the colorant may be 1 to 300 parts by weight, preferably 3 to 200 parts by weight, more preferably 5 to 150 parts by weight based on 100 parts by weight of the binder resin.

When the content of the colorant satisfies this range, the effect of light shielding may be improved, and in addition, process characteristics and electrical characteristics for pattern formation may be improved.

The black matrix photoresist composition according to the exemplary embodiment of the present invention may form a pattern through spin coating on a substrate by adding a solvent and then irradiating ultraviolet rays using a mask to develop the alkaline developer. The content of the solvent may be 10 to 3,000 parts by weight, preferably 20 to 1,000 parts by weight, more preferably 30 to 500 parts by weight, based on 100 parts by weight of the binder resin.

The solvent may be ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propion, in consideration of compatibility with binder resins, photopolymerization initiators and other compounds. Nate (EEP), ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether propionate (PGMEP), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve Acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N , N -dimethylacetamide (DMAc), N -methyl-2-pi Ralidone (NMP), γ-butylolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetraha Drawfuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, Solvents, such as heptane and an octane, can be used individually or in mixture of 2 or more types, respectively.

In addition, examples of the colorant included for application to the black matrix forming resist of the present invention include carbon black, titanium black, aniline black, and C.I. pigment black 7.

In the present invention, the black matrix photoresist composition is used as an photopolymerization initiator with an oxime ester fluorene derivative compound to suppress the effect of reducing the reflectance of the black matrix thin film and inhibiting the occurrence of color difference, and advantageously, deep curing is advantageous for the formation of a pattern. There is an advantage that can be usefully used in the manufacture of a thin film.

Hereinafter, the exemplary compounds of the present invention will be described in detail with reference to Examples and Comparative Examples for a detailed understanding of the present invention. Examples according to the present invention may be modified in various forms, and the scope of the present invention. Should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

< Production of Binder Resin>

1) Preparation of Binder Resin 1

After adding 200 mL of Propylene Glycol Methyl Ether Acetate (PGMEA) and 1.5 g of AIBN to a 500 mL polymerization vessel, 20 parts of methacrylic acid, glycidylmethacrylic acid, methylmethacrylic acid and dicyclopentanylacrylic acid were added. Solid content of the acrylic monomer was added at 40% by weight in a molar ratio of: 20: 40: 20, and then polymerized with stirring at 70 ° C. for 5 hours under a nitrogen atmosphere to prepare binder resin 1 as an acrylic polymer. The copolymer thus produced had an average molecular weight of 25,000 and a dispersion of 1.9.

 2) Preparation of Binder Resin 2

After adding 200 mL of propylene glycol methyl ether acetate and 1.0 g of AIBN to a 500 mL polymerization vessel, methacrylic acid, styrene, methylmethacrylic acid, and cyclohexyl methacrylic acid were added in a molar ratio of 40: 20: 20: 20, respectively. Was added to 40% by weight, and then polymerized by stirring with stirring at 70 ° C. for 5 hours under a nitrogen atmosphere. 0.3 g of N, N -dimethylaniline and 20 molar ratios of glycidylmethacrylic acid were added to the reactor, followed by stirring at 100 ° C. for 10 hours to prepare a binder resin 2 which is an acrylic polymer having an acrylic unsaturated bond in the side chain. The average molecular weight of the copolymer prepared as described above was confirmed to be 20, 000 and dispersion degree of 2.0.

3) Preparation of Binder Resin 3

After 200 mL of propylene glycol methyl ether acetate and 1.0 g of AIBN were added to a 500 mL polymerization vessel, glycidylmethacrylic acid, styrene, methylmethacrylic acid and cyclohexylmethacrylic acid were each acrylic in a molar ratio of 40: 20: 20: 20. A solid content of the monomer was added at 40% by weight, and then polymerized by stirring with stirring at 70 ° C. for 5 hours under a nitrogen atmosphere. To this reactor, 0.3 g of N, N -dimethylaniline and 20 molar ratios of acrylic acid were added to 100 moles of solids of the entire monomer, followed by stirring at 100 ° C. for 10 hours to prepare binder resin 3, an acrylic polymer having an acrylic unsaturated bond in the side chain. It was. The average molecular weight of the copolymer prepared as described above was 18,000, and the degree of dispersion was found to be 1.8.

4) Preparation of Binder Resin 4

62.5 g (0.05 mole) of methyl 3- (triethoxysilyl) propionate in 500 mL polymerization vessel, 51.6 g (0.04 mole) of bicyclo heptanyl triethoxy silane, methyl tri (triethoxysilyl) propionate 6.8 g (0.01 mole) of methoxy silane and 200 g of propylene glycol monomethyl ether acetate were quantified, the solution was stirred, and 10.4 g (0.02 mole) of 35% hydrochloric acid solution, 47.2 g of water, and 50 g of tetrahydrofuran were added dropwise thereto. do. After completion of the dropwise addition, the reaction temperature was raised to 85 ° C., and the reaction proceeded at the elevated temperature for 6 hours. After the completion of the reaction, tetrahydrotrofuran and methanol were evaporated off in an appropriate amount, extracted with ether and water, and the organic phase was recovered. The remaining alcohol and solvent were evaporated to remove 54g of siloxane resin. The obtained siloxane resin is dissolved in 125.5 g of propylene glycol monomethyl ether acetate. The weight average molecular weight of the obtained siloxane resin was 6,000.

5) Binder Resin 5

Cardo-based binder resin used CAP-01 (manufacturer: Miwon).

Example  1 to 17: black matrix Photoresist  Preparation of the composition

20 wt% of binder resins 1 to 5, 10 wt% of dipentaerythritol hexaacrylate, and compounds 1, 2, and 3 as photopolymerization initiators according to the components and contents shown in Table 1 in the reaction mixing tank equipped with the ultraviolet shielding film and the stirrer. 50% by weight of carbon black dispersed in PGMEA at 0.5% by weight, 25% by weight of solids and FC-430 (3M), 0.1% by weight) as a leveling agent were added sequentially and stirred at room temperature, followed by PGMEA as a solvent. Was added to a total of 100% by weight to prepare a black matrix photoresist composition.

[Compound 1]

[Compound 2]

[Compound 3]

[Compound 4]

Example  18 to 20: for solubility evaluation Photoresist  Preparation of the composition

As the photopolymerization initiator, the content of Compound 1 was added 1.0, 2.0, 3.0% by weight, and the carbon black was not added to check the solubility, and the other components and the stirring method were prepared in the same photoresist composition as in Example 2.

Example Binder Resin (20 wt%) Polymerizable Compound (10 wt%) Photopolymerization Initiator (wt%) One Binder 1 Dipentaerythritol hexaacrylate Compound 1 (0.5) 2 Binder 1 Dipentaerythritol hexaacrylate Compound 2 (0.5) 3 Binder 1 Dipentaerythritol hexaacrylate Compound 3 (0.5) 4 Binder 1 Dipentaerythritol hexaacrylate Compound 4 (0.5) 5 Binder 2 Dipentaerythritol hexaacrylate Compound 1 (0.5) 6 Binder 2 Dipentaerythritol hexaacrylate Compound 2 (0.5) 7 Binder 2 Dipentaerythritol hexaacrylate Compound 3 (0.5) 8 Binder 2 Dipentaerythritol hexaacrylate Compound 4 (0.5) 9 Binder 3 Dipentaerythritol hexaacrylate Compound 1 (0.5) 10 Binder 3 Dipentaerythritol hexaacrylate Compound 2 (0.5) 11 Binder 3 Dipentaerythritol hexaacrylate Compound 3 (0.5) 12 Binder 3 Dipentaerythritol hexaacrylate Compound 4 (0.5) 13 Binder 4 Dipentaerythritol hexaacrylate Compound 1 (0.5) 14 Binder 4 Dipentaerythritol hexaacrylate Compound 2 (0.5) 15 Binder 4 Dipentaerythritol hexaacrylate Compound 3 (0.5) 16 Binder 4 Dipentaerythritol hexaacrylate Compound 4 (0.5) 17 Binder 5 Dipentaerythritol hexaacrylate Compound 2 (0.5) 18 Binder 1 Dipentaerythritol hexaacrylate Compound 1 (1.0) 19 Binder 1 Dipentaerythritol hexaacrylate Compound 2 (2.0) 20 Binder 1 Dipentaerythritol hexaacrylate Compound 3 (3.0)

Comparative example  1 to 3: Black Matrix Photoresist  Preparation of the composition

Black matrix photoresist compositions of Comparative Examples 1 to 3 were prepared in the same manner as in Example 2, except that the following Compounds 5, 6, and 7 were used as photopolymerization initiators, respectively.

 [Compound 5]

[Compound 6]

      [Compound 7]

Comparative example  4 to 6: Solubility evaluation Photoresist  Preparation of the composition

The photoresist composition was prepared in the same manner as in Example 2, with other components and stirring methods using 1.0 wt%, 2.0 wt%, and 3.0 wt% of the compound 6 as the photopolymerization initiator and no carbon black added for solubility. Was prepared.

[Property evaluation]

Evaluation of the black matrix photoresist compositions of Examples 1 to 17 and Comparative Examples 1 to 3 was carried out on a glass substrate, and the results of evaluation of the sensitivity, pattern characteristics, sheet resistance, etc. of the photoresist composition were measured. Indicated.

1) Sensitivity

The photoresist was spin-coated on the glass substrate to form a coating film having a thickness of about 1.9 μm after the heat treatment at 100 ° C. for 90 seconds. The exposure gap was 150 μm using a photomask to measure CD (critical demension) of a pattern formed by increasing the pressure from 20 mJ / cm ² to 10 mJ / cm ² with a high pressure mercury lamp. After exposure it was developed in 0.04% KOH aqueous solution. Thereafter, the mixture was washed with pure water, dried, and post-baked in a convection oven at 230 ° C. for 30 minutes to form a black matrix pattern. The sensitivity was expressed by the sensitivity of each sample as the exposure amount at which the size of the CD (Critical demension) of the pattern was saturated.

2) Surface Hardness

After exposure and development at the exposure dose determined in the above sensitivity evaluation, the number of pinholes generated on the surface of the black matrix was determined to be less than 0 to 3, less than 3 to 7 in 10 mm X 10 mm, and more than 7 to be X.

3) Development process characteristics

After the exposure at the exposure dose determined in the above sensitivity evaluation, development was carried out to determine the development process range (BP-BT) with the developing time of the non-exposed part as BT and the peeling time of the exposed part pattern 10 µm as BP.

4) reflectance

After the black matrix composition was applied onto the substrate using a spin coater, the reflectance of the black matrix formed through a process such as prebake, exposure, and postbake was measured.

5) Solubility

Evaluation of the solubility composition prepared in Examples 18 to 20 and Comparative Examples 4 to 6, after blending the composition in a transparent glass container, and left for 48 hours at room temperature conditions excellent solubility according to the degree of turbidity of the composition, good solubility ○, the poor solubility was determined by X solubility and the results are shown in Table 2 below. Here, turbidity can be regarded as a phenomenon that occurs because precipitates occur due to a decrease in solubility when the photopolymerization initiator content is contained in an excessive amount.

Example Sensitivity Surface Hardness Developing Process Range (sec) reflectivity(%) Solubility One 60 ○ 80 6.5 - 2 80 ○ 60 6.7 - 3 90 △ 40 6.5 - 4 120 △ 30 6.7 - 5 40 ○ 110 6.4 - 6 60 ○ 70 6.4 - 7 60 ○ 70 6.5 - 8 80 △ 50 6.3 - 9 40 ○ 110 6.4 - 10 60 ○ 70 6.3 - 11 60 ○ 70 6.4 - 12 80 △ 50 6.5 - 13 60 ○ 100 5.8 - 14 80 ○ 80 5.9 - 15 90 ○ 80 6.1 - 16 120 △ 60 6.0 - 17 60 ○ 100 5.9 - 18 <40 ○ 100 - ◎ 19 <40 ○ 120 - ◎ 20 <40 ○ 120 - ◎ Comparative Example 1 150 X 10 7.4 - Comparative Example 2 70 △ 70 7.8 - Comparative Example 3 80 △ 70 7.2 - Comparative Example 4 <40 ○ 80 - ○ Comparative Example 5 <40 ○ 90 - X Comparative Example 6 <40 ○ 100 - X

Claims (7)

A black matrix photoresist composition comprising an oxime ester fluorene derivative compound represented by Formula 1 as a photopolymerization initiator: [Formula 1]

In Chemical Formula 1, R ₁ to R ₃ are each independently hydrogen, halogen, (C1-C20) alkyl, (C6-C20) aryl, (C1-C20) alkoxy, (C6-C20) aryl (C1-C20) alkyl, hydroxy ( C1-C20) alkyl, hydroxy (C1-C20) alkoxy (C1-C20) alkyl or (C3-C20) cycloalkyl; A is hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C1-C20) alkoxy, (C6-C20) aryl (C1-C20) alkyl, hydroxy (C1-C20) alkyl, hydroxy ( C1-C20) alkoxy (C1-C20) alkyl, (C3-C20) cycloalkyl, amino, nitro, cyano or hydroxy; n is 0 or 1; The method of claim 1, R ₁ to R ₃ are each independently bromo, chloro, iodo, methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, t -butyl, n -pentyl, i -pentyl, n -hexyl, i -hexyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy, n -propyloxy, i -propyloxy, n -butoxy, i -Butoxy, t -butoxy, hydroxymethyl, hydroxyethyl, hydroxy n -propyl, hydroxy n -butyl, hydroxy i -butyl, hydroxy n -pentyl, hydroxy i -pentyl, hydroxy n -Hexyl, hydroxy i -hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl And hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl. The method of claim 1, The composition is a black matrix photoresist composition comprising a binder resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator and a colorant of the formula (1). The method of claim 3, The binder resin is a black matrix photoresist composition, characterized in that at least one selected from acrylic resin, cardo resin, and silicone resin. The method of claim 3, The colorant is a black matrix photoresist composition, characterized in that at least one selected from carbon black, titanium black, acekylene black, aniline black, perylene black, strontium titanate, chromium oxide and ceria. The method of claim 3, The content of the colorant is a black matrix photoresist composition, characterized in that 1 to 300 parts by weight based on 100 parts by weight of the binder resin. The method of claim 1, The composition is one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, thiol compounds, and O-acyl oxime compounds other than the compound represented by the formula (1). Or two or more additional photopolymerization initiators.