KR20160056836A - Composition of black matrix photoresist for Liquid Crystal display panel - Google Patents

Abstract

The present invention relates to a black matrix photoresist composition for a liquid crystal display panel, which uses an excellent photopolymerization initiator to reduce the reflection ratio of a black matrix thin film, to inhibit degradation of color difference generation and to facilitate core curing and patterning, while not affecting the transmission of a liquid crystal display panel. More particularly, the photopolymerization initiator used in the present invention is an oxime ester fluorene derivative compound represented by the following chemical formula 1. In chemical formula 1, each of R_1-R_3 independently represents H, a 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 H, a (C1-C20)alkyl, C(6-C20)aryl, (C1-C20)aryl(C1-C20)alkyl, hydroxy(C1-C20)alkyl, hydroxy(C1-C20)alkoxy(c1-C20)alkyl, (C3-C20)cycloalkyl, amino, nitro, cyano or hydroxy; and n is 0 or 1.

Description

[0001] The present invention relates to a black matrix photoresist composition for a liquid crystal display panel,

The present invention relates to a black matrix which is a photosensitive resin composition for light-shielding used in a liquid crystal display. More particularly, the present invention relates to a photosensitive resin composition which can be used for producing a black matrix used in a liquid crystal display by using a photolithography method.

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

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

In general, the oxide thin film transistor minimizes the above-mentioned problems by introducing a light-shielding layer because the property of the semiconductor is changed by light. Since the light shielding layer is formed mainly of a metallic light shielding layer after the formation of the light shielding layer and the subsequent process such as PE-CVD proceeds at a high temperature, the metallic light shielding layer reflects light between the source and drain electrodes and the light shielding layer And a parasitic voltage is generated between the source and the drain electrodes, which acts as an element that resists the operation of the device and increases the load on the data line.

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

[Patent Document 1] KR 2007-0131523 (December 14, 2007) [Patent Document 2] KR 2009-0131415 (December 28, 2009) [Patent Document 3] JP 2011-247437 (Nov. 11, 2011)

Accordingly, a problem to be solved by the present invention is to provide a black matrix photoresist composition for a liquid crystal display panel which is advantageous in reducing the reflectance and inhibiting the occurrence of color difference, and being advantageous in the process of pattern formation and development, It has its purpose.

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

In Formula 1,

R ₁ to R ₃ are each independently selected from the group consisting of hydrogen, halogen, (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl (C1-C20) alkyl, hydroxy (C1-C20) alkoxy (C1-C20) alkyl or (C3-C20) cycloalkyl;

A is selected from the group consisting of hydrogen, (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl (C1-C20) alkyl, (C3-C20) cycloalkyl, amino, nitro, cyano or hydroxy;

n is 0 or 1;

The substituents including the "alkyl", "alkoxy" and other "alkyl" moieties described in the present invention include both linear and branched forms, and "cycloalkyl" includes not only a single ring system but also a plurality of cyclic hydrocarbons. &Quot; Aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination and is a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, And includes a form in which a plurality of aryls are connected by a single bond. &Quot; Hydroxyalkyl " means OH-alkyl in which a hydroxy group is bonded to an alkyl group as 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 '(C 1 -C 20) alkoxy' group is preferably (C 1 -C 10) alkoxy, more preferably (C 1 -C 4) alkoxy. The '(C6-C20) aryl (C1-C20) alkyl' group is preferably (C6-C18) aryl (C1-C10) alkyl and more preferably (C6-C18) aryl The 'hydroxy (C1-C20) alkyl' group is preferably hydroxy (C1-C10) alkyl, more preferably hydroxy (C1-C6) alkyl. The 'hydroxy (C1-C20) alkoxy (C1-C20) alkyl' group is preferably hydroxy (C1-C10) alkoxy -C6) alkyl. The '(C3-C20) cycloalkyl' group is preferably (C3-C10) cycloalkyl.

More particularly the 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 - cyclohexyl, 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, n -hexyl, hydroxy i -hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, Hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl, or hydroxyethoxyhexyl;

A is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i- butyl, t- butyl, phenyl, naphthyl, biphenyl, terphenyl anthryl, indenyl, And examples thereof include methoxy, ethoxy, propoxy, butoxy, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, Hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, amino, nitro, cyano or hydroxy, but is not limited thereto.

Examples of the oxime ester fluorene derivative compound according to the present invention include the following compounds, but the following compounds do not limit the present invention.

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

The black matrix photoresist composition of the present invention comprises the oxime ester fluorene derivative compound represented by the above formula (1), a binder resin, a polymerizable compound having an ethylenically unsaturated bond, a colorant, and the like. And is excellent in physical properties of the thin film, such as being advantageous in pattern formation due to advantage of deep curing.

As the binder resin in the black matrix photoresist composition of the present invention, an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in its side chain, an acrylic resin, a carcass resin, a silicone resin or a mixed resin thereof may be used.

The content of the binder resin can be controlled in order to control the pattern characteristics and impart thin film properties such as heat resistance and chemical resistance. For example, 3 to 50% by weight can be used for 100% by weight of the photoresist composition. The binder resin preferably has a weight average molecular weight of 2,000 to 300 and a dispersity of 1.0 to 10.0, more preferably a weight average molecular weight of 4,000 to 100,

The acrylic polymer is a copolymer of monomers comprising the following monomers: examples of such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) Acrylate, octyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (Meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate and hexadecyl (meth) acrylate, isobonyl (meth) acrylate, adamantyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) But are not limited to, acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid anhydride, maleic acid monoalkyl ester, monoalkyl itaconate, monoalkyl fumarate, glycidyl acrylate, glycidyl methacrylate, (Meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3- ethyl-3-oxetane methyl (meth) acrylate, styrene, α- methyl styrene, acetoxy-styrene, N - methyl maleimide, N - ethyl maleimide, N - propyl maleimide, N - butyl maleimide, N - (Meth) acrylamide, N -methyl (meth) acrylamide, and the like, each of which may be used alone or in combination of two or more.

The acrylic polymer having an acryl-unsaturated bond in the side chain is a copolymer obtained by addition reaction of an epoxy resin to an acrylic copolymer containing a carboxylic acid, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid monoalkyl ester, (Meth) acrylates such as methyl (meth) acrylate and hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, adamantyl Acrylate, 2-methoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl 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- An epoxy resin such as epoxybutyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate is subjected to an addition reaction at a temperature of 40 to 180 ° C A binder resin can be used.

Another example of the acrylic polymer having an acryl-unsaturated bond in the side chain is a copolymer obtained by addition reaction of a carboxylic acid to an acrylic copolymer containing an epoxy group, glycidyl acrylate, glycidyl methacrylate, 3,4- (Meth) acrylate containing an epoxy group such as epoxybutyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (Meth) acrylate such as cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, styrene,? -Methylstyrene, acetoxystyrene Alkylene, N - methyl maleimide, N - ethyl maleimide, N - propyl maleimide, N - butyl maleimide, N - cyclohexyl maleimide, (meth) acrylamide, N - monomers such as methyl (meth) acrylamide Acrylic monomer containing acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid monoalkyl ester, or other carboxylic acid and an acrylic monomer containing an epoxy group obtained by copolymerizing two or more kinds of monomers with an acrylic monomer at 40 to 180 DEG C Lt; RTI ID = 0.0 >%,< / RTI >

In addition, according to one embodiment of the present invention, a cadmium resin may be used as the binder resin, and the cadmium resin refers to an acrylic binder resin containing a fluorene group in the main chain, and is not particularly structurally limited.

The silicone resin may be a siloxane resin. More specifically, the silicone resin may be a siloxane resin disclosed in Korean Patent No. 10-1537771, and the manufacturing method may be manufactured by the method described in the patent . The siloxane resin may have an acid value in the range of 10-200 mg KOH / g resin when KOH titration is performed.

The siloxane resin usable in one embodiment of the present invention may be a siloxane resin containing a polymerization unit represented by the following formula (2) and a polymerization unit represented by the following formula (3).

(2)

XR ₄ -SiO _3/2

In 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 in total and substituted with an aryl group, an arylene group having 7 to 20 carbon atoms , Or a group having a total of 7 to 20 carbon atoms in which an alkylene group and an arylene group are connected

X is a hydroxy, a carboxylic acid, a carboxylic acid anhydride, a carboxylic acid anhydride derivative, an imide, an imide derivative, an amide, an amide derivative, an amine or a maleate,

(3)

R ₄ SiO _{(4-n) / 2}

In Formula 3,

R ₄ is independently hydrogen, a linear, branched or cyclic alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 10 carbon atoms, an unsaturated hydrocarbon group of 2 to 10 carbon atoms, or an acyloxy group of 2 to 10 carbon atoms, A plurality of R ₂ in the molecule may be the same or different from each other, n is an integer of from 0 to 3, and a polymerization unit in which n = 3 may be used in combination with another polymerization unit in which n is not 3.

The siloxane resin may be composed of 5 to 40 mol% of the polymer unit of the formula (1) and 95 to 60 mol% of the polymer unit of the formula (2) based on 100 mol% of the polymer unit of the formula (1) and the polymerization unit of the formula

Specific examples of the siloxane resin include, but are not limited to, a siloxane resin comprising a first polymerization unit represented by the following formulas (4) to (17) and a second polymerization unit listed below.

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

Examples of the monomer forming the second polymerization unit include tetraalkoxysilane, trialkoxysilane, methyltrialkoxysilane, ethyltrialkoxysilane, n-propyltrialkoxysilane, isopropyltrialkoxysilane, n-butyltrialkoxysilane , tert-butyltrialkoxysilane, phenyltrialkoxysilane, naphthatrialkoxysilane, vinyltrialkoxysilane, methacryloxymethyltrialkoxysilane, 2-methacryloxyethyltrialkoxysilane, 3-methacryloxypropyltrialkoxysilane , 3-methacryloxypropylmethyldialkoxysilane, 3-methacryloxypropylethyldialkoxysilane, acryloxymethyltrialkoxysilane, 2-acryloxyethyltrialkoxysilane, 3-acryloxypropyltrialkoxysilane, 3- Acryloxypropylmethyldialkoxysilane, 3-acryloxypropylethyldialkoxysilane, 3-glycidyloxypropyltrialkoxane Epoxycyclohexylethyltrialkoxysilane, 3-epoxycyclohexylpropyltrialkoxysilane, dimethylalkoxysilane, diethyldialkoxysilane, dipropyldialkoxysilane, diphenyldialkoxysilane, diphenylsilanediol, and Phenylmethyldialkoxysilane, and phenylmethyldialkoxysilane can be used alone or in combination of two or more. Wherein the alkoxy is a straight, branched or cyclic aliphatic or aromatic alkoxy having 1 to 7 carbon atoms and may be a hydrolyzable halogen compound.

In the black matrix photoresist composition of the present invention, the polymerizable compound having an ethylenically unsaturated bond is crosslinked by a photoreaction at the time of pattern formation to form a pattern, and is crosslinked upon heating 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 the above range, the problem of excessively increasing the 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 exemplified by methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) (Meth) acrylate, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate having a number of ethylene oxide groups of 2 to 14, ethylene glycol di (meth) acrylate, ethylene oxide Propylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, trimethylolpropane di (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylate having 2 to 14 carbon atoms, Acrylic acid adducts, phthalic acid diesters of dihydroxyethyl (meth) acrylate, toluene diisocyanates of dihydroxyethyl (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra Acrylate of a polyglycidyl compound such as a trimethylolpropane triglycidyl ether acrylic acid adduct, a compound obtained by esterifying a polyhydric alcohol and an?, Diunsaturated carboxylic acid such as dipentaerythritol tri (meth) acrylate, These may be used alone or in combination of two or more.

The amount of the oxime ester fluorene derivative compound represented by the general formula (1) contained as a photopolymerization initiator in the black matrix photoresist composition of the present invention is such that the reflectance of the black matrix is minimized, the color difference is suppressed, May be 0.01 to 50 parts by weight, preferably 0.02 to 25 parts by weight, and 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 photo-curability is ensured and the pattern is easily formed due to the difference in developability between the exposed portion and the non-exposed portion, and a T-shaped pattern due to excessively- And a desired pattern shape can be obtained.

According to one embodiment of the photoresist composition of the present invention, in addition to the oxime ester fluorene derivative compound of Formula 1, a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, a thiol compound , And an O-acyloxime compound other than the compound represented by the formula (1).

Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like can be used. Examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1- (4-morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- Examples of the nonimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Bis (2,4-dichlorophenyl) -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 compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4 (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) - 4,6-bis (trichloromethyl) -s-triazine and the like can be used.

Examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone- 1- [ Yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl- Yl) -1H-pyrazinylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime), ethanone- 1- [ 1,3-dioxoranyl) methoxybenzoyl r-9H-carbazol-3-yl] -1- (O-acetyloxime).

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

In addition, the black matrix photoresist composition of the present invention may further comprise a silicone compound having an epoxy group or an amine group as an adhesion promoter, if necessary. The silicon compound in the black matrix photoresist composition improves the adhesion between the ITO electrode and the photoresist composition and can increase the heat resistance after curing. Examples of the silicone compound having an epoxy group or an amine group include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyl (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- Methoxysilane, and aminopropyltrimethoxysilane. These may be used alone or in combination of two or more. The content of the silicone compound having an epoxy group or an 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 contain a compatibilizing additive such as a photosensitizer, a thermal polymerization inhibitor, a defoaming agent, and a leveling agent, if necessary.

The colorant of the present invention is preferably at least one selected from carbon black, titanium black, acetylacetone black, aniline black, perylene black, strontium titanate, chromium oxide and ceria which exhibit light shielding properties . 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 light shielding effect is improved, and the process characteristics and electrical characteristics for pattern formation can be improved.

A black matrix photoresist composition according to an exemplary embodiment of the present invention may be patterned by applying a solvent and spin-coating the substrate, then irradiating ultraviolet rays using a mask to develop the black matrix with an alkali 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.

In consideration of compatibility with a binder resin, a photopolymerization initiator and other compounds, the solvent may be ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxypropionate (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, (DMF), N , N -dimethylacetamide (DMAc), N -methyl-2-pyridinecarboxylic acid diacetate (NMP),? -Butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetra Propanol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, Heptane, octane, etc. may be used alone or in combination of two or more.

Examples of the coloring material to be applied to the resist for forming a black matrix of the present invention include carbon black, titanium black, aniline black, and C. I. Pigment Black 7.

The black matrix photoresist composition of the present invention is characterized in that the use of oxime ester fluorene derivative compound as a photopolymerization initiator suppresses the reflectance reduction effect and inhibition of color difference generation of the black matrix thin film, The present invention is advantageous in that it can be advantageously used in the manufacture of thin films.

For a better understanding of the present invention, representative compounds of the present invention will be described in detail with reference to Examples and Comparative Examples. However, the embodiments according to the present invention can be modified into various other forms, Should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

≪ Preparation of binder resin &

1) Preparation of Binder Resin 1

200 mL of propylene glycol methyl ether acetate (PGMEA) and 1.5 g of AIBN were added to a 500 mL polymerization vessel, and then methacrylic acid, glycidyl methacrylic acid, methyl methacrylic acid and dicyclopentanilic acrylic acid were added to 20 : 20: 40: 20, and then the mixture was stirred at 70 DEG C for 5 hours under nitrogen atmosphere to prepare binder resin 1, which is an acrylic polymer. The copolymer thus prepared had an average molecular weight of 25,000 and a degree of dispersion of 1.9.

 2) Preparation of binder resin 2

200 mL of propylene glycol methyl ether acetate and 1.0 g of AIBN were added to a 500 mL polymerization vessel, and then a solution of acrylic acid, styrene, methyl methacrylic acid, and cyclohexyl methacrylic acid in a molar ratio of 40:20:20:20, respectively, Was added in an amount of 40% by weight, and the mixture was polymerized under stirring in a nitrogen atmosphere at 70 캜 for 5 hours to synthesize a copolymer. To this reactor was added 0.3 g of N, N -dimethylaniline and 20 molar ratio of glycidyl methacrylic acid, and the mixture was stirred at 100 ° C for 10 hours to prepare an acrylic polymer having acrylic unsaturated bonds in its side chain. The average molecular weight of the copolymer thus prepared was found to be 20, 00, and the degree of dispersion was 2.0.

3) Preparation of binder resin 3

200 mL of propylene glycol methyl ether acetate and 1.0 g of AIBN were added to a 500 mL polymerization vessel and glycidyl methacrylic acid, styrene, methyl methacrylic acid, and cyclohexyl methacrylic acid were added to the acrylic resin solution at a molar ratio of 40: 20: 20: The solid content of the monomer was added in an amount of 40% by weight, and the resulting mixture was polymerized under stirring in a nitrogen atmosphere at 70 캜 for 5 hours to synthesize a copolymer. To this reactor was added 0.3 g of N, N -dimethylaniline and 20 molar ratio of acrylic acid to 100 mol of the solid content of the entire monomer, and the mixture was stirred at 100 DEG C for 10 hours to prepare an acrylic polymer having acrylic unsaturated bonds in its side chain Respectively. The copolymer thus prepared had an average molecular weight of 18,000 and a dispersion degree of 1.8.

4) Preparation of binder resin 4

A 500 mL polymerization vessel was charged with 62.5 g (0.05 mole) of methyl 3- (triethoxysilyl) propionate, 51.6 g (0.04 mole) of bicycloheptanyl triethoxysilane, 6.8 g (0.01 mole) of methoxysilane and 200 g of propylene glycol monomethyl ether acetate were weighed, and 10.4 g (0.02 mole) of 35% hydrochloric acid aqueous solution, 47.2 g of water and 50 g of tetrahydrofuran were added dropwise do. After completion of the dropwise addition, the reaction temperature was raised to 85 캜, and the reaction was carried out at the elevated temperature for 6 hours. After completion of the reaction, an appropriate amount of tetrahydrofuran and methanol was removed by evaporation, and ether and water were added to extract the organic phase. The organic phase was recovered and the residual alcohol and solvent were evaporated to obtain 54 g of a siloxane resin. The obtained siloxane resin was 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

CAP-01 (manufacturer: Miwon) was used as a cadmium binder resin.

Examples 1 to 17: Preparation of black matrix photoresist composition

20% by weight of binder resins 1 to 5, 10% by weight of dipentaerythritol hexaacrylate, 10% by weight of compounds 1, 2 and 3 as photopolymerization initiators were added to a reaction mixture tank equipped with an ultraviolet shielding film and a stirrer, , 50% by weight of carbon black dispersed in PGMEA and 0.1% by weight of FC-430 (3M Co., Ltd.) as a leveling agent), 0.5% by weight of 4, 0.5% by weight of solid content, and stirred at room temperature. Was added so that the total amount of the composition was 100% by weight to prepare a black matrix photoresist composition.

[Compound 1]

[Compound 2]

[Compound 3]

[Compound 4]

Examples 18 to 20: Preparation of photoresist composition for solubility evaluation

The same photoresist composition as in Example 2 was prepared in the same manner as in Example 2 except that 1.0, 2.0 and 3.0 wt% of Compound 1 was added as a photopolymerization initiator and carbon black was not added for solubility confirmation.

Example Binder resin
(20% by weight) Polymerizable compound
(10% by weight) Photopolymerization initiator
(weight%) 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 Examples 1 to 3: Preparation of black matrix photoresist composition

A black matrix photoresist composition of Comparative Examples 1 to 3 was prepared in the same manner as in Example 2 except that the following compounds 5, 6, and 7 were used as the photopolymerization initiator, respectively.

 [Compound 5]

[Compound 6]

      [Compound 7]

Comparative Examples 4 to 6: Preparation of photoresist composition for solubility evaluation

The other components and the stirring method were the same as in Example 2 except that 1.0, 2.0 and 3.0 wt% of the compound 6 were used as a photopolymerization initiator, respectively, and no carbon black was added for solubility confirmation. .

[Property evaluation]

The evaluation of the black matrix photoresist compositions of Examples 1 to 17 and Comparative Examples 1 to 3 was performed on a glass substrate and the performance of the photoresist composition such as sensitivity, pattern characteristics, and sheet resistance was measured, Respectively.

1) Sensitivity

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

2) Surface hardness

When the number of pinholes generated on the surface of the black matrix after exposure and development at the exposure amount determined in the sensitivity evaluation was less than 0 to less than 3 in 10 mm X 10 mm,? Was evaluated as?, Less than 3 to?

3) Development process characteristics

After the exposure at the exposure determined according to the above sensitivity evaluation, development was carried out to determine the developing process range (BP-BT) with the developing time of the unexposed portion as BT and the peeling time of 10 m of the exposed portion pattern as BP.

4) Reflectance

The black matrix composition was coated on a substrate using a spin coater, and then the reflectance of the black matrix formed through processes such as prebake, exposure, and postbake was measured.

5) Solubility

The solubility compositions prepared in Examples 18 to 20 and Comparative Examples 4 to 6 were prepared by mixing the compositions in a transparent glass container, leaving the mixture at room temperature for 48 hours, and exhibiting excellent solubility according to the degree of turbidity of the composition. And the solubility defects were determined as solubility in X and the results are shown in Table 2 below. Here, turbidity is a phenomenon that occurs when precipitates are generated due to a decrease in solubility when the photoinitiator content is excessively contained.

Example Sensitivity Surface hardness Development 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 represented by the following formula (1) as a photopolymerization initiator:
[Chemical Formula 1]

In Formula 1,
R ₁ to R ₃ are each independently selected from the group consisting of hydrogen, halogen, (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl (C1-C20) alkyl, hydroxy (C1-C20) alkoxy (C1-C20) alkyl or (C3-C20) cycloalkyl;
A is selected from the group consisting of hydrogen, (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl (C1-C20) alkyl, (C3-C20) cycloalkyl, amino, nitro, cyano or hydroxy;
n is 0 or 1; The method according to claim 1,
Wherein R ₁ to R ₃ are each independently selected from bromo, chloro, iodo, methyl, ethyl, n - propyl, i - propyl, n - butyl, i - butyl, t - butyl, n - pentyl, i - pentyl, n - hexyl, i - cyclohexyl, 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-butyl, hydroxy-n -Hexyl, hydroxy i -hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl , Hydroxyethoxybutyl, hydroxyethoxypentyl, or hydroxyethoxyhexyl. The method according to claim 1,
Wherein the composition comprises a binder resin, a polymerizable compound having an ethylenic unsaturated bond, a photopolymerization initiator of the formula (1), and a colorant. The method of claim 3,
The black matrix photoresist composition according to claim 1, wherein the binder resin is at least one selected from the group consisting of an acrylic resin, a carboxy resin and a silicone resin. The method of claim 3,
Wherein the coloring agent is at least one selected from the group consisting of carbon black, titanium black, acetylacetone black, aniline black, perylene black, strontium titanate, chromium oxide and ceria. The method of claim 3,
Wherein the content of the coloring agent is 1 to 300 parts by weight based on 100 parts by weight of the binder resin. The method according to claim 1,
Wherein the composition is at least one selected from the group consisting of a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, a thiol compound, and an O-acyloxime compound other than the compound represented by the formula Or at least two or more additional photopolymerization initiators.