KR100842168B1 - Photosensitive resin composition and liquid crystal display device using the same - Google Patents

Abstract

(A) a colorant comprising a pigment; (b) an alkali-soluble resin binder; (c) a polyfunctional monomer having an ethylenically unsaturated double bond; (d) a photopolymerization initiator; And (e) a solvent, wherein the photopolymerization initiator comprises (i) at least one initiator selected from the group consisting of a first acetophenone based photoinitiator having an absorption band in a region of 300 nm or more; (Ii) at least one initiator selected from the group consisting of a second acetophenone based photoinitiator having an absorption band in the region of 300 nm or less; And (iii) a non-imidazole-based photoinitiator group, a black matrix produced by the composition, and a liquid crystal display device comprising the black matrix.

The photosensitive composition according to the present invention can provide a bright image with high aperture ratio by realizing a fine pattern having a straight-line property by using two or more kinds of acetophenone photoinitiators and nonimidazoline photoinitiators that cause curing in different regions at the time of exposure In addition, it is possible to prevent omission, defects, and residual phenomenon on the substrate caused by the development.

Black matrix, thin film transistor, liquid crystal display, driving substrate, organic pigment, photoinitiator, photosensitive resin composition

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, and a liquid crystal display using the same. BACKGROUND ART [0002]

1 is an SEM photograph ((a) x 12,000, (b) x2,000, (c) line width image of a pattern formed by exposure (200 mJ / cm ² ) using the photosensitive resin composition of Example 1) .

FIG. 2 is a graph showing a transmittance change of a black matrix formed using the photosensitive resin composition of the present invention according to wavelengths. FIG.

3 is a UV absorption spectrum according to the wavelength of the photoinitiator used in the present invention.

The present invention relates to a photosensitive resin composition used for forming a black matrix directly on a driving substrate or on a silicon nitride film in a liquid crystal display device driven by a thin film transistor (TFT) method, a black matrix formed by the photosensitive resin composition, To a liquid crystal display device including a black matrix.

In recent years, a color liquid crystal display device using a thin film transistor has been fabricated by forming a color filter substrate on which a black matrix and a color filter are formed by using an upper plate and a thin film transistor substrate as a driving substrate provided with TFT elements and pixel electrodes corresponding to each pixel, And the two substrates are made to face each other. In this case, it is difficult to accurately align the positions, and the width of the black matrix has to be increased in order to facilitate the alignment. The larger width of the black matrix is a limitation of the improvement of the aperture ratio (the ratio of the portion through which light is transmitted). In order to obtain a brighter image, the number of light sources (backlight) must be increased, .

A color liquid crystal display device according to still another embodiment is a color liquid crystal display device in which a black matrix and a color filter layer are formed directly on a surface of a driving substrate or on a nitrated silicon film as a lower substrate and a substrate on which an ITO electrode is sputtered is used as a top substrate And in this case there is no need to align. In addition, since the line width of the black matrix can be reduced and the size thereof can be enhanced, the aperture ratio can be improved. Thus, a brighter image can be obtained even with an existing light source. However, when forming a color filter using a black matrix or a chromium black matrix using a conventional carbon black on a driving substrate, current flow is disturbed due to a low resistance value of carbon black and a high relative dielectric constant There arises a problem of display failure of the liquid crystal display device in which the portion to which the voltage is applied does not operate correctly.

In order to prevent the deterioration of the operating function of the portion to which the voltage is applied in the driving substrate on which the black matrix is formed, a coloring agent that imparts a light shielding function to the film has a low dielectric constant and a high dielectric constant instead of carbon black, There is a method of mixing organic pigments having a resistance value and / or adjusting the ratio of the organic pigments used to achieve uniform light shielding for each unit wavelength to a certain range.

However, due to the use of an organic pigment having a light-shielding property lower than that of the conventional carbon black, a large amount of an organic pigment is required to have a high optical density in a liquid crystal display device, And realization of a high aperture ratio.

The inventors of the present invention have found that it is possible to produce a fine line width for realizing a high numerical aperture and to obtain a pattern having excellent linearity by limiting the kind, amount and / or ratio of the photoinitiator among the components of the photosensitive resin composition.

Accordingly, the present invention provides a photosensitive resin composition comprising two or more acetophenone photoinitiators and a nonimidazole photoinitiator as a photopolymerization initiator, a black matrix produced by the composition, and a liquid crystal display device comprising the black matrix The purpose is to provide.

(A) a colorant comprising a pigment; (b) an alkali-soluble resin binder; (c) a polyfunctional monomer having an ethylenically unsaturated double bond; (d) a photopolymerization initiator; And (e) a solvent, wherein the photopolymerization initiator comprises (i) at least one initiator selected from the group consisting of a first acetophenone based photoinitiator having an absorption band in a region of 300 nm or more; (Ii) at least one initiator selected from the group consisting of a second acetophenone based photoinitiator having an absorption band in the region of 300 nm or less; And (iii) a non-imidazole-based photoinitiator group, a black matrix produced from the composition, and a liquid crystal display device including the black matrix.

Hereinafter, the present invention will be described in detail.

Conventional photosensitive resin compositions generally use at least one photopolymerization initiator. Specific examples thereof include a non-imidazole compound, a benzoin compound, an acetophenone compound, a benzophenone compound, an? -Diketone compound, Compounds or triazine-based compounds.

The above-mentioned photopolymerization initiators all act to generate active species that initiate polymerization of a polyfunctional monomer having an ethylenically unsaturated double bond by exposure to radiation, but the effects depending on the kind, amount and ratio thereof are somewhat different , But have not yet recognized the importance of their type, quantity and proportion.

However, in the present invention, by using a photopolymerization initiator that causes curing in different regions of the photopolymerization initiator, for example, a first acetophenone-based photoinitiator and a second acetophenone-based photoinitiator, it is possible to produce a fine line width for realizing a high numerical aperture, This excellent pattern can be realized.

<Photopolymerization initiator>

The photopolymerization initiator (d) among the constituent components of the photosensitive resin composition for a black matrix according to the present invention comprises a first acetophenone-based, second acetophenone-based, and nonimidazole-based photopolymerization initiator It is preferable to use a photoinitiator in combination.

First, as the first acetophenone-based photoinitiator, it is preferable to have an absorption band in a region of 300 nm or more, and an acetophenone-based compound having an aminoalkyl group at the? -Position is preferable. Since the .alpha.-aminoalkyl acetophenone-based photoinitiator has excellent exposure efficiency, it penetrates deeply to the lower end of the film which can not easily enter the exposure (light) and supports the polymerization pattern of the monomer. . As a result, the adhesion to the substrate is improved, and the peeling phenomenon of the film at the time of development can be solved. Non-limiting examples of the first acetophenone photoinitiator include 2-methyl- (4-methylthio) phenyl-2-morpholino-1-propan-1-one (IRGACURE 907) -1- (4-morpholinophenyl) -butan-1-one (IRGACURE 369) or mixtures thereof.

The second acetophenone type photoinitiator preferably has an absorption band in the region of 300 nm or less, and particularly preferably an acetophenone type having a hydroxy group or an alkoxy group at the? -Position. The second acetophenone type photoinitiator is a surface-curing type photoinitiator which mainly causes a photoreaction on the surface of the film because the light efficiency is not so large, and examples thereof include 2-hydroxy-2-methyl-1-phenylpropane- 1-one (darocure 1173), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan- 1-propan-1-one (Irgacure 2959), 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184), 2,2-dimethoxy-2-phenylacetophenone (IRGACURE 651), 2,2-diethoxy-2-phenylacetophenone (UVATONE 8302) or mixtures thereof.                     

Actually, as shown in FIG. 3, the first acetophenone photoinitiator (I-369, I-907) exhibits an absorption peak in the region of 300 nm or more and the second acetophenone photoinitiator (I-184, I651, ) Has an absorption band at 300 nm or less.

The content of the first acetophenone photoinitiator and the second acetophenone photoinitiator is preferably 0.1 to 5 parts by weight per 100 parts by weight of the composition, and the ratio of the first acetophenone photoinitiator and the second acetophenone photoinitiator is preferably 30:70 To 70:30. If the ratio of the first acetophenone photoinitiator and the second acetophenone photoinitiator is less than 30:70, the lower curing of the film may not occur sufficiently, resulting in poor adhesion and separation at the time of development. If the ratio exceeds 70:30, Pattern implementation can be difficult.

The other component of the photopolymerization initiator (d) constituting the photosensitive resin composition for a black matrix according to the present invention is preferably a imidazole-based photoinitiator, and non-limiting examples thereof include 2,2-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetrakis Methoxyphenyl) -1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole or mixtures thereof. Other compounds having an imidazole ring can also be used. The content of the non-imidazole-based photoinitiator is preferably in the range of 10 to 30 parts by weight per 100 parts by weight of the acetophenone-based photoinitiator.

The content of the photopolymerization initiator (d) described above is suitably 0.01 to 500 parts by weight, preferably 1 to 300 parts by weight per 100 parts by weight of the polyfunctional monomer (c) having an ethylenically unsaturated double bond. When the amount is less than 0.01 part by weight, curing by exposure may be insufficient, resulting in missing, defective or undercuts in the pattern. If the amount exceeds 500 parts by weight, the black matrix formed is likely to be separated from the substrate during development, And the like, can be generated in areas other than the area to be treated.

The photopolymerization initiator (d) according to the present invention may further comprise at least one photocrosslinking sensitizer, a curing accelerator or other additives as auxiliary components in addition to the above-mentioned two or more kinds of acetophenone photoinitiators and nonimidazoline photoinitiators.

The photocrosslinking sensitizer accelerates the generation of radicals. Nonlimiting examples thereof include benzophenone, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4 , 6-trimethylaminobenzophenone, methyl-o-benzoylbenzoate, 3,3-dimethyl-4-methoxybenzophenone, 3,3,4,4-tetra (t-butylperoxycarbonyl) Benzophenone based compounds; Fluorene-based compounds such as 9-fluorenone, 2-chloro-9-proprenone and 2-methyl-9-fluorenone; Thioxanthone systems such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propyloxytioxanthone, isopropylthioxanthone and diisopropylthioxanthone compound; Xanthone compounds such as xanthone and 2-methylxanthone; Anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; (9-acridinylpentane), 1,3-bis (9-acridinyl) propane, and the like Acridine-based compounds; Dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bicyclo [2,2,1] heptane-2,3-dione, and 9,10-phenanthrenequinone; Phosphine oxide-based compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; Benzophenone compounds such as methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate and 2-n-butoxyethyl-4- (dimethylamino) benzoate; (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone, 2,6-bis Amino-synergists such as methyl-cyclopentanone; (Diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl- -Benzoyl-7-methoxy-coumarin, 10,10-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H- Pyran o [6,7,8-ij] -quinolizine-11-one; Chalcone compounds such as 4-diethylaminokalone and 4-azidobenzalacetophenone; 2-benzoylmethylene, or 3-methyl-b-naphthothiazoline, and particularly, a benzophenone-based compound is preferable. The content of the photo-crosslinking sensitizer is preferably in the range of 5 to 30 parts by weight per 100 parts by weight of the acetophenone photoinitiator

The curing accelerator for accelerating the curing is preferably a mercapto-based compound, and non-limiting examples thereof include 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, -Dimercapto-1,3,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, pentaerythritol-tetrakis (3-mercaptopropionate), pentaerythritol- Tris (2-mercaptoacetate), trimethylolpropane-tris (2-mercaptoacetate) or trimethylolpropane-tris (2-mercaptoacetate), pentaerythritol tetrakis 3-mercaptopropionate), and the like. The content of the curing accelerator is preferably in the range of 5 to 30 parts by weight based on 100 parts by weight of the acetophenone photoinitiator.

<Colorant>

The colorant (a) among the constituents of the photosensitive resin composition according to the present invention may be a conventional pigment known in the art, and it is particularly preferable to use one or more organic pigments in combination. This is because not only the average optical density is increased but also the average optical density (OD) is uniformly adjusted for each unit wavelength to have a high light shielding property, so that the black color can be brought close to the white light source.

The organic pigment preferably has a relative dielectric constant of 10 or less and a volume resistivity of 10 ¹¹ Ω cm or more. This is because the black matrix formed on the driving substrate due to the low dielectric constant and the high resistance value of the organic pigment can prevent display failure due to current disturbance when a voltage is applied.

Non-limiting examples of the red pigment among the organic pigments having a relative dielectric constant of 10 or less and a volume resistivity of 10 ¹¹ Ω cm or more include CI PIGMENT RED 3, CI PIGMENT RED 23, CI PIGMENT RED 97, CI PIGMENT RED 108, CI PIGMENT RED 122, CI PIGMENT RED 139, CI PIGMENT RED 149, CI PIGMENT RED 166, CI PIGMENT RED 168, CI PIGMENT RED 175, CI PIGMENT RED 177, CI PIGMENT RED 180, 202, CI PIGMENT RED 214, CI PIGMENT RED 215, CI PIGMENT RED 220, CI PIGMENT RED 224, CI PIGMENT RED 230, CI PIGMENT RED 235, CI PIGMENT RED 242, CI PIGMENT RED 254, CI PIGMENT RED 255, 260, CI PIGMENT RED 262, CI PIGMENT RED 264, CI PIGMENT RED 272, or mixtures thereof.

Non-limiting examples of yellow pigments include C.I. PIGMENT yellow 13, C.I. PIGMENT yellow 35, C.I. PIGMENT yellow 53, C.I. PIGMENT yellow 83, C.I. PIGMENT yellow 93, C.I. PIGMENT yellow 110, C.I. PIGMENT yellow 120, C.I. PIGMENT yellow 138, C.I. PIGMENT yellow 139, C.I. PIGMENT yellow 150, C.I. PIGMENT yellow 154, C.I. PIGMENT yellow 175, C.I. PIGMENT yellow 180, C.I. PIGMENT yellow 181, C.I. PIGMENT yellow 185, C.I. PIGMENT yellow 194, C.I. PIGMENT yellow 213, or a mixture thereof.

Also, non-limiting examples of blue pigments include C.I. PIGMENT BLUE 15, C.I. PIGMENT BLUE 15: 1, C.I. PIGMENT BLUE 15: 3, C.I. PIGMENT BLUE 15: 6, C.I. PIGMENT BLUE 36, C.I. PIGMENT BLUE 71, C.I. PIGMENT BLUE 75 or mixtures thereof.

Also, non-limiting examples of violet pigments include C.I. PIGMENT VIOLET 15, C.I. PIGMENT VIOLET 19, C.I. PIGMENT VIOLET 23, C.I. PIGMENT VIOLET 29, C.I. PIGMENT VIOLET 32, C.I. PIGMENT VIOLET 37, etc. In addition, carbon black, white pigment, fluorescent pigment and the like may be used.

The colorant (a) is preferably used as a mixture of one or more organic pigments, and may be used in a color of black. In particular, 10 to 70 parts by weight of red pigment, 10 to 70 parts by weight of a yellow pigment, 10 to 70 parts by weight of a blue pigment and 0 to 20 parts by weight of a violet pigment are preferably used per 100 parts by weight of the pigment.

The content of the colorant (a) composed of the mixed pigment is preferably 1 to 60 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the total solid content of the photosensitive resin composition. When the content of the colorant is less than 1 part by weight, the optical density of the formed film is low and the light shielding property is not sufficient. When the amount is more than 60 parts by weight, there is a problem in developability and residue is generated.

<Alkali-soluble resin binder>

The alkali-soluble resin binder (b) among the constituents of the photosensitive composition for a black matrix according to the present invention comprises a monomer including a typical acid function known in the art; And a copolymer of a monomer copolymerizable with the monomer may be used.

Non-limiting examples of the monomer containing the acid group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmaleic acid, isoprenesulfonic acid, styrenesulfonic acid, 5- (Meth) acrylate mono (meth) acrylate mono-2 - ((meth) acryloyloxy) ethyl phthalate, mono- Or mixtures thereof.

Non-limiting examples of the monomer copolymerizable with the monomer including the acid group include styrene, chlorostyrene,? -Methylstyrene, vinyltoluene, 2-ethylhexyl (meth) acrylate, methyl (meth) (Meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, isobonyl (meth) acrylate, 2-phenoxyethyl Hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl part (Meth) acrylate, diethylamino (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2-methoxyethyl (Meth) acrylate, methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxy triethylene glycol (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p- Acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate (Meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate,? - (meth) acyloloxyethylhydrogen isocyanate, methyl? -Hydroxymethylacrylate, ethyl? Methyl acrylate, propyl? -Hydroxymethylacrylate, butyl? -Hydroxymethylacrylate, N-phenylmaleimide, N- (4-chlorophenyl) maleimide or mixtures thereof.

The alkali-soluble resin (b) of the present invention is obtained by copolymerizing the copolymer (i) and the copolymer (i) in addition to the copolymer (i) of the monomer having an acid function as described above and the monomer copolymerizable with the monomer A polymer (ii) prepared by a polymer reaction with an ethylenically unsaturated compound containing an epoxy group; A polymer (iii) prepared by a polymer reaction between the copolymer (i) and an ethylenically unsaturated compound containing an acid group; The polymer (iv) prepared through the reaction of introducing an additional acid group in addition to the polymer of (i), (ii) and / or (iii) may also be used. The copolymer (i), the polymer (ii), the polymer (iii) or the polymer (iv) may be used alone or in combination of two or more.

Non-limiting examples of the ethylenically unsaturated compound containing an epoxy group include allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2-methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-hexene, 1,2-epoxy-9-decene or mixtures thereof.

In the alkali-soluble resin of the present invention, the polymers represented by the following formula (1) are preferably used alone or in combination of two or more.

(I)

(I)

In this formula,                     

R are each independently H, CH _3, or CH ₂ OH, and;

R ₁ is an alkyl group having 1 to 18 carbon atoms or R ₆ having 1 to 10 carbon atoms including an aryl group, an aralkyl group, oxygen or nitrogen, wherein R ₆ is an alkyl group, an aryl group, an aralkyl group, An alkyl group or an aryl group having 3 to 10 carbon atoms and an aralkyl group having an unsaturated double bond such as acrylate or methacrylate and allyl;

R ₂ is H or an alkyl group having 1 to 15 carbon atoms having a carboxylic acid group at the terminal;

R ₃ is an alkyl, cycloalkyl, or aryl group having 2 to 18 carbon atoms;

R4 And R5 are each independently H or an alkyl or allyl group having 1 to 10 carbon atoms; An alkyl or allyl group having 1 to 10 carbon atoms containing oxygen or nitrogen; R4 and R5 are a cyclic group having 3 to 18 carbon atoms and a cycloalkyl group having 3 to 18 carbon atoms substituted with a heteroatom,

l is an integer from 10 to 90;

m is an integer from 5 to 50;

n is an integer from 5 to 50;

o is an integer from 0 to 50;

In the alkali-soluble resin binder represented by the above formula (1), R _{1 as a} reactive group is a group having an unsaturated group capable of being polymerized and can be produced by adding a polymer to a copolymer or a multi-component copolymer of the alkali- have.

Examples of the reactive group include glycidyl (meth) acrylate, vinylbenzyl glycidyl ether, vinyl glycidyl ether, allyl glycidyl ether, 4-methyl-4,5-epoxypentene, At least one member selected from the group consisting of propyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane,? -Glycidoxypropyltriethoxysilane and norbornyl derivatives is preferable.

The acid value of the alkali-soluble resin binder according to the present invention is preferably in the range of 50 to 300 KOH mg / g. When the acid value is less than 50, the solubility in the alkali developing solution is low, so that the development time is prolonged and the residue may remain on the substrate. If the acid value exceeds 300, the pattern is desorbed and the linearity of the pattern can not be secured. (Or T-top) whose angle exceeds 90 degrees

The weight average molecular weight of the alkali-soluble resin binder is preferably in the range of 1,000 to 200,000. When the weight-average molecular weight is less than 1,000, the binding function between the components required as the binder polymer is weak and can not withstand the physical external force at the time of development, so that the pattern is lost and basic physical properties such as heat resistance and chemical resistance can not be satisfied. When the weight average molecular weight exceeds 200,000, developability to an alkali developer is excessively decreased, and the properties of the developing process are deteriorated. In case of severe development, the development becomes impossible and the flowability becomes worse,

The alkali-soluble resin binder may be used alone or in admixture of two or more. The content of the alkali-soluble resin binder is preferably 1 to 30 parts by weight (5 to 90% by weight, based on the solid content of the resin composition) Is preferable). When the content of the alkali-soluble resin binder is less than 1 part by weight, the adhesiveness of the formed film is deteriorated. When the content of the alkali-soluble resin binder is more than 30 parts by weight, the strength and sensitivity of the formed image are lowered.

&Lt; Polyfunctional monomer having an ethylenically unsaturated double bond >

The multifunctional monomer (c) having an ethylenically unsaturated double bond among constituent components of the photosensitive resin composition for a black matrix according to the present invention is a compound having at least one addition polymerizable unsaturated group in a molecule and having a boiling point of not lower than 100 ° C or caprolactone The introduced functional monomers are preferred.

Non-limiting examples of the compound having at least one addition polymerizable unsaturated group in the molecule and having a boiling point of 100 ° C or higher include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, or phenoxyethyl Acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, neopentyl glycol (meth) acrylate, and polyfunctional monomers such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) Polyfunctional monomers such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

Examples of the polyfunctional monomer into which caprolactone is introduced include KAYARAD DPCA-20, 30, 60, 120 and FA-2D, FA1DT and FA-3 which are introduced into dipentaerythritol, and tetrahydrofuryl acrylate KAYARAD TC-110S, KAYARAD HX-220 and KAYARAD HK-620 which are introduced into neopentyl glycol hydroxy pivalate. Other usable multifunctional monomers include epoxy acrylates of bisphenol A derivatives, novolak-epoxy acrylates, and urethane-based multi-functional acrylates such as U-324A, U15HA and U-4HA.

The above-mentioned polyfunctional monomer having an ethylenically unsaturated double bond can be used alone or in combination of two or more.

The content of the polyfunctional monomer having an ethylenically unsaturated double bond according to the present invention is preferably 1 to 30 parts by weight (including 5 to 50% by weight based on the solid content of the resin composition) per 100 parts by weight of the entire photosensitive resin composition. When the content is less than 1 part by weight, the photosensitivity or the strength of the coating film is lowered. When the content is more than 30 parts by weight, the photosensitive resin layer is excessively tacky and the strength of the film is insufficient.

<Solvent>

The solvent (e) in the constituent components of the photosensitive resin composition for a black matrix according to the present invention is preferably used in consideration of solubility, pigment dispersibility and coating properties, and examples thereof include propylene glycol monomethyl ether, ethylene Propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 2-hydroxyethyl propionate, 3 Methyl-3-methoxypropionate, ethyl-3-methoxypropionate, methyl-3-ethoxypropionate, ethyl-3-ethoxypropionate, butyl acetate, amylpermate, Isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, ethyl pyruvate, gamma-butyrolactate or mixtures thereof.

In addition to the above-described components, the photosensitive resin composition of the present invention may optionally contain at least one additive selected from the group consisting of a dispersant, an adhesion promoter, an antioxidant, an ultraviolet absorber, a thermal polymerization inhibitor and a leveling agent.

The dispersing agent may be a polymer type, a nonionic, an anionic or a cationic dispersing agent. Non-limiting examples of the dispersing agent include polyalkylene glycols and esters thereof, polyoxyalkylene polyhydric alcohols, ester alkylene oxide adducts, alcohol alkyl Sulfonic acid salts, carboxylic acid esters, carboxylic acid salts, alkylamide alkylene oxide adducts, alkyl amines, or mixtures thereof. The above-mentioned dispersing agent can be used according to a conventional method known in the art, and it is particularly preferable to use the method of internally adding the pigment to the pigment in advance in a form of surface treatment or externally adding to the pigment.

Non-limiting examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) -silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane , N- (2-aminoethyl) -3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- glycidoxypropylmethyldimethoxysilane , 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (4-methoxycyclohexyl) ethyltrimethoxysilane, 3- Mercaptopropyltrimethoxysilane, mixtures thereof, and the like.

The antioxidant may be 2,2-thiobis (4-methyl-6-t-butylphenol), or 2,6-g, t-butylphenol, -5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole or alkoxybenzophenone. Further, the thermal polymerization inhibitor may be at least one selected from the group consisting of hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t- butylcatechol, benzoquinone, 4,4- -Butylphenol), 2,2-methylenebis (4-methyl-6-t-butylphenol), or 2-mercaptoimidazole.

The photosensitive resin composition according to the present invention comprises (a) 1 to 50 parts by weight of a colorant, which comprises a pigment, based on 100 parts by weight of the photosensitive resin composition; (b) 1 to 30 parts by weight of an alkali-soluble resin binder; (c) 1 to 30 parts by weight of a polyfunctional monomer having an ethylenically unsaturated double bond; (d) 1 to 30 parts by weight of a photopolymerization initiator comprising two or more acetophenone photoinitiators and a nonimidazoline photoinitiator; And (e) 30 to 90 parts by weight of a solvent.

The photosensitive resin composition according to the present invention can be prepared by a conventional method known in the art.

Hereinafter, the photosensitive composition of the present invention is applied to a driving substrate, for example, a driving thin film transistor (TFT) substrate directly or through a nitrided silicon film, followed by exposure and development .

First, 1) a photosensitive resin composition for a black matrix according to the present invention is applied directly to a substrate or to a nitrided silicon film.                     

As a method of applying the composition on the substrate, a roll coater, a curtain coater, a spin coater, a slot die coater, various printing, and deposition methods known in the art can be used have. Further, it is also possible to apply the composition onto a support such as a film and then transfer it onto another support, and the application method thereof is not particularly limited.

The applied thickness is not particularly limited and is the same as the conventional range.

2) A black matrix is prepared by exposing the applied photosensitive resin layer through a photomask having a desired pattern, and then developing the exposed photosensitive resin layer with an appropriate developer.

The irradiation energy of the radiation is suitably 100 to 5,000 J / m ² , particularly 200 to 2,000 J / m ² .

Nonlimiting examples of the alkali developing solution which can be used include an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline and the like, and an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, can do. As the development treatment method, a shower development method, a spray development method, a dip (immersion) development method, a puddle (liquid immersion) development method, and the like can be applied. The present invention provides a black matrix formed using the photosensitive resin composition and a driving substrate formed on the silicon film directly or nitrided by the black matrix.

The thickness of the black matrix is preferably in the range of 1.0 to 5.0 mu m, and the average optical density (OD) of the black matrix is preferably 3.0 or more.

Actually, the black matrix produced by using the photosensitive resin composition of the present invention exhibited a uniform optical density of 3.0 or more at specific wavelengths (450 nm, 550 nm, and 610 nm), showed almost no loss of fine patterns, There was no contamination, the pattern straightness, and the surface flatness were excellent.

Further, the present invention provides a liquid crystal display device comprising a driving substrate formed with a black matrix formed of the photosensitive resin composition formed on a silicon film directly or nitrided.

The liquid crystal display device includes the above-described black matrix and color filter, and can be manufactured according to a conventional method known in the art.

The liquid crystal display device including the black matrix can improve the aperture ratio and obtain a bright image due to the fine pattern formed and can exhibit good light shielding property even when a high luminance light source is used as the backlight, It is possible to show the high definition of the panel. Further, by using a radiation-sensitive composition containing one or more organic pigments having a low dielectric constant and a high resistance, display failure due to voltage application does not occur.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Examples 1 to 3] Photosensitive resin composition and production of liquid crystal display device]

Example 1

(Preparation of Photosensitive Resin Composition for Black Matrix)

240 parts by weight of a red pigment dispersion (CI PIGMENT RED 177, pigment component 15%), 240 parts by weight of a yellow pigment dispersion (CI PIGMENT YELLOW 139, pigment component 15%), a blue pigment dispersion (CI PIGMENT BLUE 15: 6, 300 parts by weight of a pigment component (15%), and 40 parts by weight of a violet pigment dispersion (CI PIGMENT VIOLET 23, pigment component 10%) were put in a mixer and mixed with an alkali-soluble resin binder. 55 parts by weight of a copolymer (molar ratio 70/30, Mw = 30,000) and a polymer to which glycidyl methacrylate was added in a copolymer of benzyl (meth) acrylate / (meth) acrylic acid / (meth) 20 parts by weight of polyvinyl alcohol, 20 parts by weight of polyvinyl alcohol, 24/8, and Mw = 22,000, 60 parts by weight of dipentaerythritol hexaacrylate as a functional monomer, 2 parts by weight of 2-benzyl 2- (dimethylamino) ) Butyl-1-one, 15 parts by weight of 2,2-dimethoxy-2-phenylacetophenone, 6 parts by weight of bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole, 6 parts by weight of 4,4-bis (diethylamino) benzophenone, And 3 parts by weight of mercaptobenzothiazole, 3 parts by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter and 1 part by weight of leveling agent as additives, 220 parts by weight of propylene glycol monomethyl ether acetate as a solvent, Propionate were mixed. Then, the mixture was stirred for 5 hours to prepare a photosensitive resin composition for a black matrix.

(Manufacture of a driving substrate on which a black matrix is formed)

The prepared photosensitive resin composition solution was spin-coated on a glass substrate on which a driving thin film transistor was mounted or a glass substrate on which a silicon nitride film was sputtered, and heat-treated at about 90 캜 for 2 minutes to form a coating film . The formed coating film was cooled at room temperature, and then exposed to light with an energy of 200 mJ / cm 2 under a high-pressure mercury lamp with an exposure gap of 100 m using a photomask. The exposed substrate was developed in a 0.04% KOH aqueous solution at 25 ° C by spraying method, washed with pure water, dried and post-baked in a convection oven at 220 ° C for 30 minutes.

The resulting coating film pattern had a coating film thickness of 2.8 mu m with almost no loss of pattern, no contamination of the exposed portion, and excellent pattern straightness and surface flatness. The resolution of Line / space was 10 탆 or less (see FIG. 1).

In addition, uniform light shielding characteristics were exhibited according to specific wavelengths (450 nm, 550 nm, and 610 nm), and the average optical density was 3.0 or more, showing excellent light shielding properties (FIG. 2). The value of relative dielectric constant was 4.5, the surface electric resistivity value was 10 ¹⁴ Ω / cm 2 or more, and the volume electric resistivity was 10 ¹³ Ω cm or more.

(Manufacture of a liquid crystal display device provided with a driving substrate on which a black matrix is formed)

A color filter was formed on the driving substrate having the black matrix formed thereon, and then a module was manufactured using the substrate, and a clean image without display defect due to current disturbance was obtained when a voltage was applied.

Example 2

15 parts by weight of 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) butyl-1-one as a photopolymerization initiator, 15 parts by weight of 1-hydroxycyclohexyl phenyl ketone, Except that 6 parts by weight of bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole was used in place of the black matrix A liquid crystal display device having the driving substrate and the driving substrate having the photosensitive composition for the light-sensitive resin composition, the black matrix on which the composition was photocured directly or on the nitrated silicon film was prepared.

The pattern formed using the photosensitive resin composition solution had a thickness of 2.7 탆, and the substrate on which the black matrix was formed had little loss of pattern and no contamination of the exposed portions. In addition, the resolution of the line / space was 10 μm or less, and the linearity of the pattern and the surface flatness were excellent. In addition, uniform light shielding characteristics were exhibited at specific wavelengths (450 nm, 550 nm, and 610 nm), and the average optical density was 3.0 or more, showing excellent light shielding properties. The value of relative dielectric constant was 4.5, the surface electric resistivity value was 10 ¹⁴ Ω / cm 2 or more, and the volume electric resistivity was 10 ¹³ Ω cm or more.

A color filter was formed on the driving substrate having the black matrix formed thereon, and then a module was manufactured using the substrate, and a clean image without display defect due to current disturbance was obtained when a voltage was applied.

Example 3

15 parts by weight of 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) butyl-1-one as a photopolymerization initiator, 2 parts by weight of 2-hydroxy- 15 parts by weight of 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole, , A liquid crystal display device comprising a photosensitive substrate composition for a black matrix, a driving substrate on which a photopolymerized black matrix was directly or nitrided, and a driving substrate was prepared.

The pattern formed using the photosensitive resin composition solution had a thickness of 2.8 mu m, and the substrate on which the black matrix was formed had little loss of pattern and no contamination of the exposed portion. In addition, the resolution of the line / space was 10 μm or less, and the linearity of the pattern and the surface flatness were excellent. It showed uniform light shielding characteristic according to each specific wavelength (450 nm, 550 nm, 610 nm) and showed excellent light shielding property with an average optical density of 3.0 or more. The value of relative dielectric constant was 4.5, the surface electric resistivity value was 10 ¹⁴ Ω / cm 2 or more, and the volume electric resistivity was 10 ¹³ Ω cm or more.

A color filter was formed on the driving substrate on which the black matrix was fabricated, and a module was manufactured using the substrate. When a voltage was applied, a clean image free from display failure due to current disturbance was obtained.

[Comparative Examples 1 to 3]

Comparative Example 1

30 parts by weight of 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) butyl-1-one as a photoinitiator, 30 parts by weight of 2,2'- Except that 10 parts by weight of 5,5'-tetraphenyl-1,2'-biimidazole was used in place of the photosensitive resin composition for black matrix in Example 1. The photosensitive resin composition for black matrix and the black matrix A driving substrate formed on a silicon film directly or nitrided.

The pattern formed using the photosensitive resin composition solution had a film thickness of 2.8 탆. The substrate on which the black matrix was formed had little loss of pattern, no contamination of the exposed portion, and excellent surface flatness. However, Showed a resolving power of about 30 탆.

Comparative Example 2

30 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photoinitiator, 10 parts by weight of 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl- , A photosensitive substrate composition for a black matrix and a substrate for driving, in which a photopolymerized black matrix of the composition was directly or nitrided, was formed on a silicon substrate.

The pattern formed using the photosensitive resin composition solution had a film thickness of 2.8 탆, but defects of the pattern occurred and the developing margin was worsened and the linearity deteriorated.

Comparative Example 3

5 parts by weight of 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) butyl-1-one as a photoinitiator, 25 parts by weight of 2,2-dimethoxy- 6 parts by weight of 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole, 4 parts by weight of 4,4-bis (diethylamino) benzophenone 6 Except that the above-mentioned composition was used in place of the above-mentioned photosensitive resin composition for a black matrix, and a black substrate on which the photopolymerized photopolymerization of the composition was directly or nitrided was formed on a silicon substrate Respectively.

The pattern formed using the photosensitive resin composition solution had a film thickness of 2.8 탆, but defects of the pattern occurred and the developing margin was worsened and the linearity deteriorated.

The photosensitive composition according to the present invention can provide a bright image with a high aperture ratio due to the implementation of a fine pattern having a straight line by using two or more kinds of acetophenone photoinitiators and imidazoline photoinitiators which have different actions, It is possible to prevent missing, defects and residual phenomenon on the substrate, which are generated during development.

Claims (15)

(a) a colorant containing at least one organic pigment having a dielectric constant of 10 or less, or a volume resistivity of 10 ¹¹ Ω cm or more (provided that carbon black is not included); (b) an alkali-soluble resin binder; (c) a polyfunctional monomer having an ethylenically unsaturated double bond; (d) a photopolymerization initiator; And (e) Solvent Wherein the photopolymerization initiator is at least one selected from the group consisting of (I) at least one initiator selected from the group consisting of a first acetophenone based photoinitiator having an absorption band in a region of 300 nm or more in ultraviolet wavelength; (Ii) at least one initiator selected from the group consisting of a second acetophenone based photoinitiator having an absorption band in the region of less than 300 nm in the ultraviolet wavelength; And (Iii) a non-imidazole-based photoinitiator group. The composition of claim 1, wherein the first acetophenone based photoinitiator has an aminoalkyl group at the? -Position. 2. The composition of claim 1 wherein the first acetophenone based photoinitiator is selected from the group consisting of 2-methyl- (4-methylthio) phenyl-2-morpholino-1-propan- Dimethylamino-1- (4-morpholinophenyl) -butan-1-one (IRGACURE 369). The composition of claim 1, wherein the second acetophenone based photoinitiator has a hydroxy group or an alkoxy group at the? -Position. 2. The composition of claim 1 wherein the second acetophenone based photoinitiator is selected from the group consisting of 2-hydroxy-2-methyl-1-phenylpropan-1-one (darocure 1173), 1- (DAROCURE 1116), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-di-methyl-1-propan- Irgacure 2959), 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184), 2,2-dimethoxy-2-phenylacetophenone (IRGACURE 651) and 2,2- &Lt; / RTI &gt; The composition of claim 1, wherein the ratio of the first acetophenone system to the second acetophenone photoinitiator is from 30:70 to 70:30. 3. The composition of claim 1 wherein the imidazole photoinitiator is selected from the group consisting of 2,2-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'- Phenyl) -4,4 ', 5,5'-tetrakis (3,4,5-trimethoxyphenyl) -1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl ) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl- And at least one member selected from the group consisting of polysaccharides and polysaccharides. The composition of claim 1, wherein the non-imidazole photoinitiator is 10 to 30 parts by weight per 100 parts by weight of the acetophenone photoinitiator. The composition according to claim 1, wherein the photopolymerization initiator (d) comprises 5 to 30 parts by weight of a mercapto-based curing accelerator and 5 to 20 parts by weight of a benzophenone-based sensitizer. delete The composition according to claim 1, wherein 10 to 70 parts by weight of a red pigment, 10 to 70 parts by weight of a yellow pigment, 10 to 70 parts by weight of a blue pigment, and 0 to 20 parts by weight of a violet pigment are contained in 100 parts by weight of the pigment. The composition according to claim 1, wherein the alkali-soluble resin binder (b) is represented by the following general formula (I)

(I) In this formula, R are each independently H, CH _3, or CH ₂ OH, and; R ₁ is an alkyl group having 1 to 18 carbon atoms or R ₆ having 1 to 10 carbon atoms including an aryl group, an aralkyl group, oxygen or nitrogen, wherein R ₆ is an alkyl group, an aryl group, an aralkyl group, An alkyl group or an aryl group having 3 to 10 carbon atoms and an aralkyl group having an unsaturated double bond such as acrylate or methacrylate and allyl; R ₂ is H or an alkyl group having 1 to 15 carbon atoms having a carboxylic acid group at the terminal; R ₃ is an alkyl, cycloalkyl, or aryl group having 2 to 18 carbon atoms; R4 And R5 are each independently H or an alkyl or allyl group having 1 to 10 carbon atoms; An alkyl or allyl group having 1 to 10 carbon atoms containing oxygen or nitrogen; R4 and R5 are a cyclic group having 3 to 18 carbon atoms and a cycloalkyl group having 3 to 18 carbon atoms substituted with a heteroatom; l is an integer from 10 to 90; m is an integer from 5 to 50; n is an integer from 5 to 50; o is an integer from 0 to 50; The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition comprises (a) 1 to 50 parts by weight of a colorant comprising a pigment, (b) 1 to 30 parts by weight of an alkali-soluble resin binder; (c) 1 to 30 parts by weight of a polyfunctional monomer having an ethylenically unsaturated double bond; (d) 1 to 30 parts by weight of a photopolymerization initiator comprising two or more acetophenone photoinitiators and a nonimidazoline photoinitiator; And (e) 30 to 90 parts by weight of a solvent. A black matrix formed by the photosensitive resin composition of any one of claims 1 to 9 and 11 to 13. A liquid crystal display comprising a black matrix formed by the photosensitive resin composition of any one of claims 1 to 9 and 11 to 13.

Images