KR20070079085A - Photosensitive resin composition and liquid crystal display device using the same - Google Patents

Abstract

A photosensitive resin composition is provided to embody a fine pattern having straightness, produce bright images of a high aperture ratio, and prevent omissions and losses of a pattern and a remaining phenomenon on a substrate. A photosensitive resin composition comprises (a) a coloring agent including pigments, (b) an alkali-soluble resin binder, (c) a multi-functional monomer having an ethylenically unsaturated double bond, (d) a photopolymerization initiator, and (e) a solvent. The photopolymerization initiator contains a mixture of (i) at least one initiator selected from the first acetophenone-based photo initiator group having an absorption band in the ultraviolet wavelength region of 300nm or longer, (ii) at least one initiator selected from the second acetophenone-based photo initiator group having an absorption band in the ultraviolet wavelength region below 300nm, and (iii) at least one selected from the biimidazole-based photo initiator group.

Description

Photosensitive resin composition and a liquid crystal display using the same {PHOTOSENSITIVE RESIN COMPOSITION AND LIQUID CRYSTAL DISPLAY DEVICE USING THE SAME}

The present invention relates to a photosensitive resin composition used to form 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, A liquid crystal display device comprising a black matrix.

Recently, a color liquid crystal display using thin film transistors manufactures a color filter substrate on which a black matrix and a color filter are formed on a top plate, and a thin film transistor substrate, which is a driving substrate having TFT elements and pixel electrodes corresponding to each pixel on a bottom plate. It is manufactured by making two substrates face each other. In this case, it was difficult to align the position accurately, and the width of the black matrix was forced to be large for easy alignment. Increasing the width of the black matrix is the limit of improvement of the aperture ratio (the ratio of the part of the light transmitted), and in order to obtain a brighter image, the number of light sources (backlights) must be increased, which requires more power consumption and weight. There is a drawback to this.

A color liquid crystal display device according to another embodiment uses a black matrix and a color filter layer formed directly on a surface of a driving substrate or on a nitrided silicon film as a lower plate, and uses a substrate on which an ITO electrode is sputtered as an upper plate. To be bonded together, which does not need to be aligned. In addition, since the line width of the black matrix can be reduced and fixed, the aperture ratio can be improved, and thus, a brighter image can be obtained even with a conventional light source. However, when a color filter is formed by using a black matrix or a chromium black matrix using a conventional carbon black on a driving substrate, the current flow is disturbed when voltage is applied due to the low resistance value and the high dielectric constant of the carbon black. The problem of poor display of the liquid crystal display device, such as a portion in which the voltage is applied does not operate correctly occurs.

In order to prevent the deterioration of the operation function of the part where the voltage is applied in the driving substrate on which the black matrix is formed, it is a colorant which gives a light shielding role of the film and has a low dielectric constant and a high dielectric constant instead of carbon black having a low resistance value and a high relative dielectric constant. There is a method of adjusting the ratio of the organic pigment used in order to mix and use the organic pigment which has a resistance value, and / or to have uniform light-shielding property for each unit wavelength.

However, due to the use of organic pigments having a lower light shielding property than the conventional carbon black, a large amount of organic pigment blending is required in order for the liquid crystal display to have a high optical density. There will be constraints on implementation and realization of high opening rates.

The present inventors have found that by limiting the type, amount and / or ratio of photoinitiators in the photosensitive resin composition constituents, it is possible to produce a fine line width for achieving a high opening ratio and to obtain a pattern having excellent straightness.

Accordingly, the present invention provides a photosensitive resin composition, a black matrix prepared by the composition, and a liquid crystal display device comprising the black matrix, wherein at least two acetophenone-based photoinitiators and biimidazole photoinitiators are used as photopolymerization initiators. It aims to provide.

The present invention (a) a colorant comprising a pigment; (b) alkali-soluble resin binders; (c) a polyfunctional monomer having an ethylenically unsaturated double bond; (d) photopolymerization initiators; And (e) a solvent, wherein the photopolymerization initiator comprises (i) at least one initiator selected from the group of first acetophenone-based photoinitiators having an absorption band in a region of 300 nm or more in the ultraviolet wavelength; (Ii) at least one initiator selected from the group of second acetophenone-based photoinitiators having an absorption band in the region of less than 300 nm in the ultraviolet wavelength; And (iii) at least one member selected from the group of biimidazole-based photoinitiators, a black matrix prepared from the composition, and a liquid crystal display device comprising the black matrix.

The photosensitive composition according to the present invention may provide a bright image with a high opening ratio due to the realization of a fine pattern having straightness by mixing two or more acetophenone-based photoinitiators and biimidazole photoinitiators having different functions. In addition, it is possible to prevent missing patterns, defects, and residual phenomenon on the substrate generated during development.

Hereinafter, the present invention will be described in detail.

Conventionally, the photosensitive resin composition generally uses one or more photopolymerization initiators, and specific examples thereof include biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, and phosphine compounds. Compounds or triazine compounds.

All of the above-described photopolymerization initiators act to generate active species which initiate the polymerization of polyfunctional monomers having ethylenically unsaturated double bonds by exposure to radiation, but the effects of the kind, amount and ratio thereof vary slightly. In addition, the importance of their type, quantity and ratio has not been recognized to date.

However, in the present invention, by mixing a photopolymerization initiator, such as a first acetophenone-based photoinitiator and a second acetophenone-based photoinitiator, which causes curing in different regions among the photopolymerization initiators, it is possible to produce a fine line width to realize a high opening ratio and go straight. This excellent pattern can be implemented.

<Photoinitiator>

Among the components of the photosensitive resin composition for a black matrix according to the present invention, the photopolymerization initiator (d) is a first acetophenone-based, a second acetophenone-based, and a biimidazole-based compound which causes a curing reaction in different regions to form a fine pattern. It is preferable to mix photoinitiators.

First, the first acetophenone-based photoinitiator preferably has an absorption band in a region of 300 nm or more, and an acetophenone-based compound having an aminoalkyl group at the α-position is preferable. Since the α-aminoalkyl acetophenone-based photoinitiator is excellent in exposure efficiency, it penetrates deeply to the bottom of the film where exposure (light) cannot easily enter and supports the polymerization pattern of the monomer, and hardens well to the bottom of the film. Make it happen. For this reason, adhesiveness with a board | substrate improves and the peeling phenomenon of the film at the time of image development can be solved. Non-limiting examples of the first acetophenone-based photoinitiator is 2-methyl- (4-methylthio) phenyl-2-morpholino-1-propan-1-one (IRGACURE907), 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butan-1-one (IRGACURE369) or mixtures thereof.

The second acetophenone-based photoinitiator preferably has an absorption band in the region of 300 nm or less, and an acetophenone-based compound having a hydroxy group or an alkoxy group at the α-position is particularly preferable. The second acetophenone-based photoinitiator is a surface-curable photoinitiator that mainly causes a photoreaction on the surface of the film because the light efficiency is not so great, non-limiting examples thereof are 2-hydroxy-2-methyl-1-phenylpropane- 1-one (darocure 1173), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (DAROCURE 1116), 1- [4- (2-hydroxyethoxy)- Phenyl] -2-hydroxy-di-2methyl-1-propan-1-one (Irgacure 2959), 1-hydroxycyclohexylphenylketone (IRGACURE 184), 2,2-dimethoxy-2-phenylacetophenone (IRGACURE 651), 2,2-diethoxy-2-phenylacetophenone (UVATONE 8302), or mixtures thereof.

In fact, as shown in FIG. 3, the first acetophenone-based photoinitiators (I-369, I-907) exhibit absorption peaks in a region of 300 nm or more, and the second acetophenone-based photoinitiators (I-184, I651, d-1173). ) Can be seen to have an absorption band below 300nm.

The content of the first acetophenone-based photoinitiator and the second acetophenone-based photoinitiator is preferably 0.1 to 5 parts by weight per 100 weight of the composition, and in particular, the use ratio of the first acetophenone-based photoinitiator and the second acetophenone-based photoinitiator is 30:70. To 70:30 is preferred. When the ratio of the first acetophenone-based photoinitiator and the second acetophenone-based photoinitiator is less than 30:70, hardening of the lower end of the film may not occur well, resulting in deterioration of adhesion and peeling during development. Pattern implementation can be difficult.

The other of the photoinitiator (d) component which comprises the photosensitive resin composition for black matrices which concerns on this invention is a biimidazole type photoinitiator, A non-limiting example of these is 2, 2-bis (2-chlorophenyl). -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetrakis (3,4,5-tri Methoxyphenyl) -1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'- Bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole or mixtures thereof. In addition, the compound which has an imidazole ring can also be used. The content of the biimidazole-based photoinitiator is preferably in the range of 10 to 30 weight per 100 weight of the acetophenone-based photoinitiator described above.

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 having (c) an ethylenically unsaturated double bond. If it is less than 0.01 part by weight, curing by exposure may be insufficient, resulting in a missing, missing or undercut in the pattern. If it exceeds 500 parts by weight, the formed black matrix is easily peeled from the substrate during development, and the pattern is formed. Background contamination, film residues, etc., may be produced in areas other than those areas.

Photoinitiator (d) according to the present invention, in addition to the two or more acetophenone-based photoinitiator and the biimidazole photoinitiator described above, may be used in combination of one or more photocrosslinking sensitizers, curing accelerators or other additives as an auxiliary component.

Photocross-linking sensitizers promote radical generation, non-limiting examples of which are 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 and the like Benzophenone compounds; Fluorenone compounds such as 9-florenone, 2-chloro-9-prorenone, and 2-methyl-9-florenone; Thioxanthones such as thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone and diisopropyl thioxanthone 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-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinylpentane), 1,3-bis (9-acridinyl) propane Acridine-based compounds; Dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bicyclo [2,2,1] heptane-2,3-dione, 9,10-phenanthrenequinone; Phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide; Benzophenone compounds such as methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate and 2-n-butoxyethyl-4- (dimethylamino) benzoate; 2,5-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone, 2,6-bis (4-diethylaminobenzal) -4- Amino synergists such as methyl-cyclopentanone; 3,3-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3 -Benzoyl-7-methoxy-coumarin, 10,10-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-C1] -benzo Coumarin-based compounds such as pyrano [6,7,8-ij] -quinolizine-11-one; Chalcone compounds such as 4-diethylamino chalcone and 4-azidebenzalacetophenone; 2-benzoylmethylene, 3-methyl-b-naphthothiazoline, and the like, and a benzophenone compound is particularly preferable. The content of the photocrosslinking sensitizer is preferably in the range of 5 to 30 weight per 100 weight of acetophenone-based photoinitiator.

In addition, a hardening accelerator for promoting hardening is preferably a mercapto-based compound, and non-limiting examples thereof include 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, 2,5 -Dimercapto-1,3,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, pentaerythritol-tetrakis (3-mercaptopropionate), pentaerythritol-tris (3-mercap Topropionate), pentaerythritol-tetrakis (2-mercaptoacetate), pentaerythritol-tris (2-mercaptoacetate), trimethylolpropane-tris (2-mercaptoacetate) or trimethylolpropane-tris ( 3-mercaptopropionate). The amount of the curing accelerator is preferably in the range of 5 to 30 weight based on 100 weight of acetophenone-based photoinitiator.

<Colorant>

As the coloring agent (a) in the constituent components of the photosensitive resin composition according to the present invention, conventional pigments known in the art may be used, and it is particularly preferable to mix one or more organic pigments. 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, thereby providing a high light shielding property, thereby bringing a black color closer to the white light source.

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

Non-limiting examples of red pigments among the organic pigments having a relative dielectric constant of 10 or less and a volume resistivity of 10 ¹¹ Ωcm or more include CI PIGMENT RED 3, CI PIGMENT RED 23, CI PIGMENT RED 97, CI PIGMENT RED 108, and 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, CI PIGMENT RED 185, CI PIGMENT RED 190, CI PIGMENT RED 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, CI PIGMENT RED 260, CI PIGMENT RED 262, CI PIGMENT RED 264, CI PIGMENT RED 272 or mixtures thereof.

In addition, 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 mixtures thereof.

In addition, 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.

In addition, 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, carbon black, white pigments, fluorescent pigments, etc. may also be used.

It is preferable to use a coloring agent (a) as the mixed liquid which mixed 1 or more types of organic pigments, and can use it, making the color black. In particular, it is preferable to use 10 to 70 parts by weight of red pigment, 10 to 70 parts by weight of yellow pigment, 10 to 70 parts by weight of blue pigment, and 0 to 20 parts by weight of violet pigment per 100 parts by weight of 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 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 not low enough to have sufficient light shielding properties, and when it exceeds 60 parts by weight, there is a problem in developability and residues are generated.

<Alkali-soluble resin binder>

Among the constituents of the photosensitive composition for black matrices according to the present invention, the alkali-soluble resin binder (b) may include a monomer including a conventional acid function known in the art; And copolymers of monomers copolymerizable with the monomers.

Non-limiting examples of the monomer containing an acid group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid, 5-norbornene- 2-carboxylic acid, mono-2-((meth) acryloyloxy) ethyl phthalate, mono-2-((meth) acryloyloxy) ethyl succinate, ω-carboxy polycaprolactone mono (meth) acrylic Rate or mixtures thereof.

Non-limiting examples of monomers copolymerizable with the monomer containing an acid group include styrene, chloro styrene, α-methyl styrene, vinyltoluene, 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, and ethyl (meth) Acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate , Dicyclopentanyl (meth) acrylate, isobonyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydroperpril (meth) acrylate, hydroxyethyl (meth) acrylate, 2- Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy part (Meth) acrylate, dimethylaminomethyl (meth) acrylate, diethylamino (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2-methoxyethyl ( Meth) acrylate, 3-methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene Glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth ) Acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate , Heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, β- (meth) acyloloxyethylhydrogen susinate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxy Methyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, N-phenylmaleimide, N- (4-chlorophenyl) maleimide or mixtures thereof.

Alkali-soluble resin (b) of the present invention is the copolymer (i) in addition to the copolymer (i) of the monomer (monomer) containing the acid function (acid function) described above and the monomer copolymerizable with the monomer. Polymer (ii) prepared by polymer reaction with an ethylenically unsaturated compound containing an epoxy group; A polymer prepared by polymer reaction with the copolymer (i) and an ethylenically unsaturated compound containing an acid group; It is also possible to use polymers (iv) prepared through the reaction of introducing additional acid groups in addition to the polymers of (i), (ii) and / or (iii) above. The said copolymer (i), the polymer (ii), the polymer (iv), or the polymer (iv) can be used individually, respectively, and can also mix and use 2 or more types.

Non-limiting examples of the ethylenically unsaturated compound containing the epoxy group include allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-no Bodene-2-methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-hexene, 1,2-epoxy-9-decene or mixtures thereof and the like.

It is preferable to use the alkali-soluble resin of this invention individually or in mixture of 2 or more types of polymers represented by following General formula (1).

(I)

(I)

Where

Each R is independently H, CH ₃ , or CH ₂ OH;

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 An alkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group having an unsaturated double bond such as a group, an acrylate or methacrylate, or 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 allyl group having 2 to 18 carbon atoms;

R4 And each R 5 is 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, R5 is a cyclic group having 3 to 18 carbon atoms which are cyclic ring or a cyclo group having 3 to 18 carbon atoms in which a hetero atom is substituted,

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 Chemical Formula 1, R _{1, which} is a reactor, is a group having an unsaturated group capable of polymerization, and may be prepared by adding a reactor to a copolymer or a multi-component copolymer of the alkali-soluble resin binder described above by a polymer reaction. have.

Reactors that can be used include glycidyl (meth) acrylate, vinyl benzylglycidyl ether, vinyl glycidyl ether, allylglycidyl ether, 4-methyl-4,5-epoxypentene, γ-glycidoxy It is preferable to select at least 1 type from the group which consists of a propyl trimethoxysilane, (gamma)-glycidoxy propyl methyl diethoxysilane, (gamma)-glycidoxy propyl triethoxy silane, and a norbornyl derivative.

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. If the acid value is less than 50, the solubility in the alkaline developer is low, so that the development time may be long, and residues may remain on the substrate. If the acid value is more than 300, the pattern may be desorbed, and the pattern may not go straight. You will see an inverse taper (or T-top) over 90 degrees.

In addition, the weight average molecular weight of the alkali-soluble resin binder is preferably in the range of 1,000 to 200,000. If the weight average molecular weight is less than 1,000, the binding function between the components required as the binder polymer is weak, and the pattern is lost due to the physical external force during development, and the physical properties such as basic heat resistance and chemical resistance cannot be satisfied. If the weight average molecular weight exceeds 200,000, the developability of the alkaline developer is excessively low, so that the development process characteristics are deteriorated, and if it is severe, the development is impossible, and the flowability becomes poor, making it difficult to control the coating thickness or to secure the uniformity of the thickness.

The above-mentioned alkali-soluble resin binder can be used individually or in mixture of 2 or more types, The content of alkali-soluble resin binder is 1-30 weight part per 100 weight part of total photosensitive resin compositions (5 to 90 weight% based on solid content of a resin composition). It is preferred to include). If the content of the alkali-soluble resin binder is less than 1 part by weight, the adhesion of the formed film is lowered, and if it exceeds 30 parts by weight, there is a problem that the strength and sensitivity of the formed image is lowered.

<Multifunctional monomer having ethylenically unsaturated double bond>

The polyfunctional monomer (c) having an ethylenically unsaturated double bond in the constituents of the photosensitive resin composition for black matrices according to the present invention contains a compound or caprolactone having a boiling point of 100 ° C. or higher having at least one unsaturated polymerizable group in the molecule. Introduced functional monomers are preferred.

Non-limiting examples of compounds having at least one or more addition-polymerizable unsaturated groups in the molecule and having a boiling point of 100 ° C. or more include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, or phenoxyethyl ( Polyfunctional monomers such as meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, neopentyl glycol (meth) acrylate, And polyfunctional monomers such as pentaerythritol tetra acrylate, pentaerythritol triacrylate, dipentaerythritol penta acrylate, or dipentaerythritol hexa acrylate.

In addition, the polyfunctional monomers in which caprolactone is introduced include KAYARAD DPCA-20, 30, 60, 120, and FA-2D, FA1DT, FA-3, and the like introduced in dipentaerythritol, and tetrahydrofuryl acrylate. KAYARAD TC-110S introduced or KAYARAD HX-220 and KAYARAD HK-620 introduced to neopentylglycol hydroxy pivalate. Other polyfunctional monomers that can be used include epoxy acrylates of bisphenol A derivatives, novolac-epoxy acrylates, and urethane-based polyfunctional acrylates, such as U-324A, U15HA, and U-4HA.

The polyfunctional monomer which has the said ethylenically unsaturated double bond can use the above-mentioned compound individually or in mixture of 2 or more types.

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 solids of the resin composition) per 100 parts by weight of the total 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 adhesiveness of the photosensitive resin layer is excessive, and thus the strength of the film is not sufficient, and there is a problem in that the pattern is lost during development.

<Solvent>

The solvent (e) in the constituent components of the photosensitive resin composition for black matrices according to the present invention is preferably used in consideration of solubility, pigment dispersibility and applicability, and non-limiting examples thereof include propylene glycol monomethyl ether, Ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 2-hydroxyethylpropionate, 3-methyl-3-methoxybutylpropionate, 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, γ-butyrol acetate or mixtures thereof.

In addition to the above-mentioned components, the photosensitive resin composition of the present invention may optionally include at least one additive selected from the group consisting of dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, thermal polymerization inhibitors and leveling agents.

Dispersants may use polymeric, nonionic, anionic or cationic dispersants, including, but not limited to, polyalkylene glycols and esters thereof, polyoxyalkylene polyhydric alcohols, esteralkylene oxide adducts, alcoholalkyls Ethylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylates, alkylamide alkylene oxide adducts, alkylamines or mixtures thereof. The aforementioned dispersant may be used according to conventional methods known in the art, and in particular, it is preferable to use the method of adding the pigment internally to the pigment or externally adding the pigment in the form of surface treatment in advance.

Non-limiting examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) -silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane , N- (2-aminoethyl) -3-aminopropylmethyltrimethoxy silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 2- (3,4-ethoxy cyclohexyl) ethyltrimethoxysilane, 3-chloropropyl methyldimethoxysilane, 3-chloropropyl trimethoxy silane, 3-methacryloxypropyltrimethoxysilane, 3- Mercaptopropyltrimethoxysilane or mixtures thereof.

The antioxidant may be 2,2-thiobis (4-methyl-6-t-butylphenol), or 2,6-g, t-butylphenol, and the ultraviolet absorber is 2- (3-t-butyl -5-methyl-2-hydroxyphenyl) -5-chloro- benzotriazole or alkoxy benzophenone can be used. In addition, the thermal polymerization inhibitor may be hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogarol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t -Butylphenol), 2,2-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptoimidazole, etc. can be used.

The photosensitive resin composition according to the present invention is based on 100 parts by weight of the photosensitive resin composition (a) 1 to 50 parts by weight of a colorant containing a pigment; (b) 1 to 30 parts by weight of an alkali-soluble resin binder; (c) 1 to 30 parts by weight of a multifunctional monomer having an ethylenically unsaturated double bond; (d) 1 to 30 parts by weight of a photopolymerization initiator comprising at least two acetophenone-based photoinitiators and biimidazole photoinitiators; And (e) 30 to 90 parts by weight of the solvent.

The photosensitive resin composition according to the present invention may prepare a black matrix according to conventional methods known in the art.

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

First, 1) The photosensitive resin composition for black matrices which concerns on this invention is apply | coated directly to a board | substrate or the nitrided silicon film.

As a method for applying the composition on a substrate, a roll coater, curtain coater, spin coater, slot die coater, various printing, deposition, or the like known in the art may be used. have. Moreover, after apply | coating on support bodies, such as a film, it is also possible to transfer on other support bodies, The application method is not specifically limited.

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

2) The black matrix is manufactured by exposing through the photomask which has a desired pattern to the apply | coated photosensitive resin layer, and developing the exposed photosensitive resin layer with a suitable developing solution.

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

Non-limiting examples of the alkaline developer that can be used include aqueous solutions 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 or ethanol or a surfactant is added to the developer. can do. In addition, as the development method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid immersion) development method, and the like can be applied. The present invention provides a black matrix manufactured using the photosensitive resin composition and a driving substrate formed on a silicon film in which the black matrix is directly or nitrided.

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

Indeed, the black matrix prepared using the photosensitive resin composition of the present invention exhibited a uniform optical density of 3.0 or more at each specific wavelength (450 nm, 550 nm, 610 nm), and showed little loss of fine patterns as well as unexposed areas. There was no contamination, and the pattern straightness and surface flatness were very excellent.

The present invention also provides a liquid crystal display device comprising a driving substrate formed on a silicon film in which a black matrix formed by the photosensitive resin composition is directly or nitrided.

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

The liquid crystal display device having the black matrix can obtain a bright image by improving the aperture ratio due to the formed fine pattern, and can exhibit good light blocking property even when a light source having a high brightness is used as the backlight, and by high surface roughness High precision of the panel can be shown. In addition, by using a radiation sensitive composition comprising at least one organic pigment having a low dielectric constant and a high resistance, display defects due to voltage application do not occur.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

[ Example  1 to 3. Photosensitive Resin Composition and Liquid Crystal Display Device Manufacturing]

Example  One

(Photosensitive resin composition manufacture for black matrices)

240 parts by weight of red pigment dispersion (CI PIGMENT RED 177, pigment component 15%), 240 parts by weight of yellow pigment dispersion (CI PIGMENT YELLOW 139, pigment component 15%), blue pigment dispersion (CI PIGMENT BLUE 15: 6, 300 parts by weight of the pigment component 15%) and 40 parts by weight of the violet pigment dispersion (CI PIGMENT VIOLET 23, pigment component 10%) were placed in a mixer and mixed with an alkali-soluble resin binder to benzyl (meth) acrylate / (meth) acrylic acid. 55 weight part of copolymer (molar ratio 70/30, Mw = 30,000) and the polymer which glycidyl methacrylate was added to the copolymer of benzyl (meth) acrylate / (meth) acrylic acid / (meth) acrylic acid (molar ratio 68 / 24/8, Mw = 22,000) 20 parts by weight, 60 parts by weight of dipentaerythritol hexaacrylate as a functional monomer, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl as a photopolymerization initiator 15 parts by weight of butyl-1-one, 15 parts by weight of 2,2-dimethoxy-2-phenylacetophenone, 2,2 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, an adhesion promoter as an additive, 1 part by weight of leveling agent, 220 parts by weight of propylene glycol monomethyl ether acetate as a solvent, ethoxyethyl 80 parts by weight of propionate was mixed. Then, the mixture was stirred for 5 hours to prepare a photosensitive resin composition for a black matrix.

(Manufacture of driving substrate with black matrix formed)

The prepared photosensitive resin composition solution was spin-coated on the glass on which the driving thin film transistor was placed or on the glass on which the silicon nitride film was sputtered thereon, and heat-treated at about 90 ° C. for 2 minutes to form a coating film having a thickness of about 3.2 μm. Formed. The formed coating film was cooled at room temperature, and then exposed to an energy of 200 mJ / cm 2 under a high pressure mercury lamp with an exposure gap of 100 µm using a photomask. The exposed substrate was developed by spraying in a 0.04% KOH aqueous solution at a temperature of 25 ° C., washed with pure water, dried, and post-baked in a convection oven at 220 ° C. for 30 minutes.

The obtained coating film pattern had a coating film thickness of 2.8 μm, almost no loss of the pattern, no contamination of the unexposed part, and the pattern was very excellent in straightness and surface flatness. In addition, the resolution of the line / space was 10㎛ or less (see Fig. 1).

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

(Manufacture of liquid crystal display device provided with driving substrate having black matrix formed)

When a color filter was formed on the driving substrate on which the black matrix was formed, a module was fabricated using the substrate to obtain a clean image without display defects due to current disturbance when a voltage was applied.

Example  2

15 parts by weight of 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) butyl-1-one as the photopolymerization initiator, 15 parts by weight of 1-hydroxycyclohexylphenylketone, 2,2 ' A black matrix was prepared in the same manner as in Example 1, except that 6 parts by weight of -bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole was used. A liquid crystal display device comprising a photosensitive resin composition for use, a driving substrate formed on a silicon film in which the black matrix on which the composition is photopolymerized is directly or nitrided, and a driving substrate.

The pattern produced using the photosensitive resin composition solution had a thickness of 2.7 μm, and the substrate on which the black matrix was formed had almost no loss of pattern and no contamination of the unexposed part. In addition, the resolution of the line / space was less than 10㎛, the pattern of the linearity and surface flatness was very excellent. In addition, it showed uniform light-shielding characteristics according to each specific wavelength (450nm, 550nm, 610nm), the average optical density was 3.0 or more showed excellent light-shielding properties. The dielectric constant was 4.5, the surface electrical resistivity value was 10 ¹⁴ Pa / cm 2 or more, and the volume electrical resistivity was 10 ¹³ Pa / cm or more, showing excellent insulation.

When a color filter was formed on the driving substrate on which the black matrix was formed, a module was fabricated using the substrate to obtain a clean image without display defects caused by current disturbance when a voltage was applied.

Example  3

15 parts by weight of 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) butyl-1-one and 2-hydroxy-2-methyl-1-phenylpropan-1-one as photopolymerization initiator Example 1, except that 15 parts by weight, 6 parts by weight of 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole was used By performing the same method as described above, a liquid crystal display including a photosensitive resin composition for a black matrix, a driving substrate formed on a silicon film on which the black matrix to which the composition was photopolymerized is directly or nitrided was manufactured.

The pattern prepared using the photosensitive resin composition solution had a thickness of 2.8 μm, and the substrate on which the black matrix was formed had little loss of pattern and no contamination of the unexposed part. In addition, the resolution of the line / space was 10 µm or less, and the linearity and surface flatness of the pattern were very excellent. It showed uniform shading characteristics according to each specific wavelength (450nm, 550nm, 610nm) and showed excellent shading property with average optical density of 3.0 or more. The dielectric constant was 4.5, the surface electrical resistivity value was 10 ¹⁴ Pa / cm 2 or more, and the volume electrical resistivity was 10 ¹³ Pa / cm or more, showing excellent insulation.

When a color filter was formed on a driving substrate on which the black matrix was manufactured through a process, a module was manufactured using the substrate to obtain a clean image without display defects due to current disturbance when a voltage was applied.

[Comparative Examples 1-3]

Comparative example  One

30 parts by weight of 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) butyl-1-one as a photoinitiator, 2,2'-bis (o-chlorophenyl) -4,4, Except for using 10 parts by weight of 5,5'-tetraphenyl-1,2'-biimidazole, the same method as in Example 1 was carried out to form a photosensitive resin composition for a black matrix and a black matrix photopolymerized A driving substrate formed on the silicon film directly or nitrided was prepared.

The pattern prepared using the photosensitive resin composition solution had a coating thickness of 2.8 μm, and the substrate on which the black matrix was formed had almost no loss of pattern, no contamination of unexposed areas, and had excellent surface flatness, but had excellent line / space resolution. Has a resolution of about 30㎛.

Comparative example  2

30 parts by weight of 1-hydroxycyclohexylphenyl ketone as a photoinitiator, 10 parts by weight of 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole Except that the portion was used, the same method as in Example 1 was performed to prepare a driving substrate formed on the silicon film on which the photosensitive resin composition for the black matrix and the black matrix to which the composition was photopolymerized was directly or nitrided.

The pattern prepared using the photosensitive resin composition solution had a coating film thickness of 2.8 μm, but it was confirmed that defects in the pattern occurred and development margin was low, resulting in deterioration of straightness.

Comparative example  3

5 parts by weight of 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) butyl-1-one as the photoinitiator, 25 parts by weight of 2,2-dimethoxy-2-phenylacetophenone, 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole 6 parts by weight, 4,4-bis (diethylamino) benzophenone 6 Except for using a weight part, the same method as in Example 1 was performed to prepare a driving substrate formed on the silicon film on which the photosensitive resin composition for black matrix and the black matrix to which the composition was photopolymerized were directly or nitrided. It was.

The pattern prepared using the photosensitive resin composition solution had a coating film thickness of 2.8 μm, but it was confirmed that defects in the pattern occurred and development margin was low, resulting in deterioration of straightness.

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

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

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

Claims (15)

(a) a colorant comprising a pigment; (b) alkali-soluble resin binders; (c) a polyfunctional monomer having an ethylenically unsaturated double bond; (d) photopolymerization initiators; And (e) solvent In the photosensitive resin composition containing, the photoinitiator is (Iii) at least one initiator selected from the group of first acetophenone-based photoinitiators having an absorption band in a region of 300 nm or more in the ultraviolet wavelength; (Ii) at least one initiator selected from the group of second acetophenone-based photoinitiators having an absorption band in the region of less than 300 nm in the ultraviolet wavelength; And (Iii) The photosensitive resin composition characterized by mixing at least 1 type selected from the group of biimidazole type photoinitiators. The composition of claim 1, wherein the first acetophenone-based photoinitiator has an amino alkyl group in the α-position. The method of claim 1, wherein the first acetophenone-based photoinitiator is 2-methyl- (4-methylthio) phenyl-2-morpholino-1-propan-1-one (IRGACURE907) and 2-benzyl-2- At least one composition selected from the group consisting of dimethylamino-1- (4-morpholinophenyl) -butan-1-one (IRGACURE369). The composition of claim 1, wherein the second acetophenone-based photoinitiator has a hydroxy group or an alkoxy group in the α-position. The method of claim 1, wherein the second acetophenone-based photoinitiator is 2-hydroxy-2-methyl-1-phenylpropan-1-one (darocure 1173), 1- (4-isopropylphenyl) -2-hydroxy Hydroxy-2-methylpropan-1-one (DAROCURE 1116), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-di-2methyl-1-propan-1-one ( Irgacure 2959), 1-hydroxycyclohexylphenyl ketone (IRGACURE 184), 2,2-dimethoxy-2-phenylacetophenone (IRGACURE 651) and 2,2-diethoxy-2-phenylacetophenone (UVATONE 8302) At least one composition selected from the group consisting of. The composition of claim 1, wherein the ratio of the first acetophenone-based and the second acetophenone-based photoinitiator is 30:70 to 70:30. The biimidazole photoinitiator of claim 1, wherein the biimidazole photoinitiator is a 2,2-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (o-chloro Phenyl) -4,4 ', 5,5'-tetrakis (3,4,5-trimethoxyphenyl) -1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl ) -4,4 ', 5,5'-tetraphenyl biimidazole and 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetrafenyl-1,2'-ratio At least one composition selected from the group consisting of imidazoles. The composition of claim 1, wherein the biimidazole photoinitiator is 10 to 30 parts by weight per 100 parts by weight of acetophenone-based photoinitiator. The composition of 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. The composition according to claim 1, wherein the pigment (a) is a pigment mixture containing one or more organic pigments having a dielectric constant of 10 or less or a resistance value of 10 ¹¹ Pa or more. The composition according to claim 1, wherein the composition comprises 10 to 70 parts by weight of red pigment, 10 to 70 parts by weight of yellow pigment, 10 to 70 parts by weight of blue pigment, and 0 to 20 parts by weight of violet pigment. The composition of claim 1, wherein the alkali-soluble resin binder (b) is represented by the following general formula (I):

(I) Where Each R is independently H, CH ₃ , or CH ₂ OH; 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 An alkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group having an unsaturated double bond such as a group, an acrylate or methacrylate, or 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 allyl group having 2 to 18 carbon atoms; R4 And each R 5 is 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, R5 is a cyclo group having 3 to 18 carbon atoms in which a cyclic ring or a hetero group having 3 to 18 carbon atoms in which a hetero atom is substituted; 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 method of claim 1, wherein the photosensitive resin composition (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 multifunctional monomer having an ethylenically unsaturated double bond; (d) 1 to 30 parts by weight of a photopolymerization initiator comprising at least two acetophenone-based photoinitiators and biimidazole photoinitiators; And (e) 30 to 90 parts by weight of the solvent. The black matrix formed by the photosensitive resin composition of any one of claims 1 to 13. The liquid crystal display device containing the black matrix formed by the photosensitive resin composition of any one of Claims 1-13.

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