KR102028582B1

KR102028582B1 - A colored photosensitive resin composition

Info

Publication number: KR102028582B1
Application number: KR1020130132921A
Authority: KR
Inventors: 이현보; 김훈식
Original assignee: 동우 화인켐 주식회사
Priority date: 2013-11-04
Filing date: 2013-11-04
Publication date: 2019-10-04
Also published as: KR20150051446A

Abstract

The present invention relates to a colored photosensitive resin composition, and more particularly, includes (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photoinitiator, and (E) a solvent. (A) the colorant comprises a mixture of an organic pigment and a black pigment containing at least one selected from the group consisting of pigment violet 29, pigment violet 31 and pigment violet 37, thereby changing color, residual film rate and optical density. Relates to an excellent colored photosensitive resin composition.

Description

Colored photosensitive resin composition {A COLORED PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a colored photosensitive resin composition, and more particularly, to a colored photosensitive resin composition having a small color change rate and a high residual film ratio.

Recently, liquid crystal displays have been spotlighted as next generation advanced display devices having low power consumption, good portability, high technology value, and high added value.

Among the liquid crystal display devices, an active matrix liquid crystal display device having a thin film transistor, which is a switching element that can control voltage on / off for each pixel, has the best resolution and video performance. It is attracting attention.

In general, an LCD device forms an array substrate and a color filter substrate through an array substrate manufacturing process for forming a thin film transistor and a pixel electrode, and a color filter substrate manufacturing process for forming a color filter and a common electrode, respectively. It completes through the liquid crystal cell process through a liquid crystal between them.

Column spacers are formed in the liquid crystal cell to maintain a constant cell gap. Column spacers have constraints such as thickness variation (dimension stability) with respect to external pressure generated in the cell process, chemical resistance to etchant, strip liquid, etc., and reactivity with liquid crystal molecules. Recently, the column spacer has a black photosensitive resin composition. It is formed.

In addition, the color filter includes pixels composed of red (R), green (G), and blue (B) colors. In order to prevent mixing of different colors or to hide patterns of electrodes in each pixel, A black matrix is formed at the boundary between the colored layers of color, which is formed of a black photosensitive resin composition.

The basic characteristics required for the black photosensitive resin composition are excellent in optical density (OD) and excellent in electrical insulation in order to impart high light shielding properties. In addition, it is preferable that the color change is small and the residual ratio is high for more effective display characteristics.

The black photosensitive resin composition has been commonly used for carbon black as a colorant, but carbon black has a disadvantage of low electrical resistance. Therefore, although it is applied as a high-resistance material through the surface treatment of carbon, in the case of carbon black, when it is made of a colored photosensitive resin composition, it is difficult to control the improvement of the dielectric constant due to the properties of the carbon material, and it is near infrared (Near-IR). The transmittance characteristic is very bad.

Therefore, a method of using a combination of organic pigments has been developed. In the case of using only an organic pigment in combination, shading of visible rays is not sufficient, and the increase of the pigment ratio causes problems of sensitivity, pattern characteristics, color change, and residual film ratio. May cause difficulty in pattern shape.

Korean Patent Publication No. 2010-66197 discloses a black photosensitive resin composition, and a light shielding layer and a column spacer using the same.

Patent Document 1: Korea Patent Publication No. 2010-66197

An object of this invention is to provide the coloring photosensitive resin composition which is low in color change rate, and excellent in a residual film rate and an optical density.

Another object of the present invention is to provide a curable pattern such as a color filter, a black matrix, a column spacer, and the like, and an image display device including the same using a colored photosensitive resin composition.

1. (A) a coloring agent, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photoinitiator, and (E) solvent, The said (A) coloring agent is pigment violet 29, pigment violet 31. And a mixture of a black pigment and an organic pigment comprising at least one selected from the group consisting of pigment violet 37. The colored photosensitive resin composition.

2. according to the above 1, wherein the organic pigment is 30 to 95% by weight, and the black pigment is 5 to 70% by weight based on the total weight of the colorant solids, the coloring photosensitive resin composition.

3. according to the above 1, wherein at least one selected from the group consisting of pigment violet 29, pigment violet 31 and pigment violet 37 is contained in 10 to 40% by weight relative to the total weight of the organic pigment, coloring photosensitive Resin composition.

4. according to the above 1, wherein the organic pigment further comprises Pigment Blue 15: 6, coloring photosensitive resin composition.

5. according to the above 1, wherein the black pigment is carbon black, coloring photosensitive resin composition.

6. Photocuring pattern is prepared by the coloring photosensitive resin composition of the above 1 to 5.

7. The photocuring pattern of claim 6, wherein the photocuring pattern is at least one selected from the group consisting of a color filter, a black matrix, and a column spacer.

8. The image display device including the photocuring pattern of the above six.

The coloring photosensitive resin composition of the present invention uses at least one of pigment violet 29, pigment violet 31, and pigment violet 37 as a colorant, while maintaining high light shielding properties and having low color change rate, and excellent residual film ratio and optical density. I can keep it. Moreover, the coloring photosensitive resin composition of this invention is excellent in near-infrared transmittance.

This invention contains (A) coloring agent, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photoinitiator, and (E) solvent, The said (A) coloring agent is pigment violet 29, pigment It is related with the coloring photosensitive resin composition excellent in color change rate, residual film rate, and optical density by including the mixture of the black pigment and the organic pigment containing at least 1 sort (s) chosen from the group which consists of violet 31 and pigment violet 37.

The coloring photosensitive resin composition of this invention can contain (A) coloring agent, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photoinitiator, and (E) solvent. Of course, it does not limit the additional inclusion of additional components such as additives commonly used in the art.

Colorant (A)

The colorant according to the present invention includes, as essential components, an organic pigment and a black pigment including at least one selected from the group consisting of pigment violet 29, pigment violet 31, and pigment violet 37.

The composition of the present invention may exhibit low color change rate, high residual film rate and excellent optical density by including the mixed pigment as a colorant.

In the present invention, at least one selected from the group consisting of pigment violet 29, pigment violet 31 and pigment violet 37 is preferably contained in 10 to 40% by weight based on the total weight of the organic pigment. When the content is less than 15% by weight, the shielding may be lowered, and when the content is higher than 40% by weight, the optical density may be lowered.

In the present invention, the organic pigment is 30 to 95% by weight, and the black pigment is preferably contained in 5 to 70% by weight based on the total weight of the colorant solids. Within this range, optical density and near-infrared transmittance can be maximized.

The black pigment usable in the present invention may be used without particular limitation to the black pigment used in the art, for example, CI pigment black 1 and 7, carbon black, etc. may be used alone or in combination of two or more, respectively. Preferably carbon black can be used.

The colorant according to the present invention may further include pigments and dyes used in the art in addition to the aforementioned pigments without departing from the object of the present invention.

The colorant according to the present invention may be included in an amount of 3 to 50% by weight based on the total weight of solids in the colored photosensitive resin composition. When a coloring agent is contained in the said range, color reproducibility and near-infrared transmittance are favorable.

(a1) pigment

Pigments (a1) which can be further used in the present invention include organic pigments and inorganic pigments.

As the organic pigment, various pigments used in printing ink, inkjet ink, and the like may be used. Specifically, phthalocyanine (aqueous azo pigment, insoluble azo pigment), phthalocyanine pigment, quinacridone pigment, isoin Dolanone pigments, isoindolin pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthhraquinonyl pigments, anthrapyrimidine pigments, ananthrone pigments, indanthrone pigments, Pravantron pigments, pyranthrone pigments or diketopyrrolopyrrole pigments and the like.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specifically, oxides or composites of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony Metal oxides; and the like.

In particular, the organic pigments and inorganic pigments include compounds that are specifically classified as pigments in the color index (published by The society of Dyers and Colourists), and more specifically, the following color index (CI) numbers Although a pigment is mentioned, It is not necessarily limited to these.

As the pigment used in the pigment dispersion composition according to the present invention, an organic pigment or an inorganic pigment generally used in the art may be used, and these may be used alone or in combination of two or more kinds.

If necessary, the pigment may be a resin treatment, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the surface of the pigment with a high molecular compound or the like, an atomization treatment by a sulfate atomization method or the like to remove impurities. The washing treatment with an organic solvent or water, the removal of ionic impurities by an ion exchange method, or the like may be performed.

Specific examples of the pigment,

C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185 ;

C.I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264;

C.I. Pigment violet 14, 19, 23, 32, 33, 36 and 38;

C.I. Pigment blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 64, and 76;

C.I. Pigment green 7, 10, 15, 25, 36, 47 and 58;

CI Pigment Brown 28; Etc. can be mentioned.

C.I. exemplified above. Among pigment pigments, C.I. Pigment Blue 15: 6, C.I. Pigment Red 177 may be preferably used.

It is preferable to use the pigment dispersion liquid which the said particle size disperse | distributed uniformly. As an example of the method for uniformly dispersing the particle size of the pigment, a method of containing and dispersing the pigment dispersant may be used. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

In the coloring photosensitive resin composition of this invention, the said (a1) pigment can be contained in the form of a pigment dispersion composition.

The pigment dispersion composition includes (a1) a pigment, (a2) a dispersant, (a3) a dispersing aid, and (a4) a dispersing solvent, and (a5) a dispersing resin may be added to facilitate storage stability and dispersion.

In addition, the pigment (a1) may be included in the range of 20 to 90% by weight, preferably 30 to 70% by weight based on the total weight of the solid content in the pigment dispersion composition. If the content of the pigment is not included in the above range is high viscosity, poor storage stability, low dispersion efficiency adversely affects the contrast ratio.

(a2) dispersant

The dispersant is added to maintain the stability of the pigment and deagglomeration can be used without limitation to those commonly used in the art. The dispersant preferably includes an acrylate dispersant (hereinafter referred to as an acrylate dispersant) including butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Commercially available products of the acrylate-based dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150, and the like. Each of the acrylate-based dispersants may be used alone or in combination of two or more thereof. Can be.

The dispersant according to the present invention may use a pigment dispersant of another resin type in addition to the acrylate-based dispersant. The other resin type pigment dispersants include known resin type pigment dispersants, in particular polycarboxylic acid esters represented by polyurethanes, polyacrylates, unsaturated polyamides, polycarboxylic acids, amine salts of polycarboxylic acids, Ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of polycarboxylic acids substituted with hydroxyl groups and modified products thereof, free carboxyl groups Amides or salts thereof formed by the reaction of polyesters with poly (lower alkyleneimines), (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate ester copolymers, styrene-maleic acid copolymers Water-soluble resins or water-soluble polymer compounds such as polymers, polyvinyl alcohol, polyvinyl pyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide and phosphate esters.

Commercially available products of the resin type pigment dispersant include cationic resin dispersants, for example, the trade names of BYK (BIC) Chemisa: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK. -164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; Product name of BASF Corporation: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Kawaken Fine Chemical's trade names: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Trade names: AJISPUR PB-821, Azisper PB-822, Azisper PB-823; The brand names of Kyoeisha Chemical Co., Ltd. are: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORON DOPA-33, FLORON DOPA-44, and the like.

The dispersant is included in an amount of 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the pigment in the colorant. If the dispersant exceeds 60 parts by weight, the viscosity may be increased. If the dispersant is less than 5 parts by weight, it may be difficult to atomize the pigment, or may cause problems such as gelation after dispersion.

In addition to the dispersant described above, surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine based may be used as the dispersant, and these may be used alone or in combination of two or more.

Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and polyethyleneimines. And KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Mega Pack (MEGAFAC) (manufactured by Dainippon Ink & Chemicals Co., Ltd.), Florard (manufactured by Sumitomo 3M Inc.), Asahi guard, Suflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE ) (Manufactured by Geneva Co., Ltd.), EFKA (manufactured by EFKA Chemicals Co., Ltd.), PB 821 (manufactured by Ajinomoto Co., Ltd.), and the like.

(a3) Dispersion Aids

Dispersion aid refers to a formulation that serves to prevent reagglomeration by dispersing the pigment into fine particles. The dispersing aid is effective in forming a colored layer having a high contrast ratio and excellent transmittance.

Dispersion aids usable in the present invention include, for example, 1,8-diamino-4,5-dihydroxyanthraquinone, 1,5-bis {[2- (diethylamino) ethyl] amino} anthra- 9,10-quinone, 1,8-bis (benzamido) anthraquinone, 1,4-bis {[2- (4-hydroxyphenyl) ethyl] amino} anthra-9,10-quinone, 1,4 -Bis {[2- (dimethylamino) ethyl] amino} -5,8-dihydroxyanthra-9,10-quinone, 1,8-dihydroxy-4- [4- (2-hydroxyethyl ) Anilino] -5-nitroanthra-9,10-quinone, 1,4-dihydroxyanthraquinone, 1,4-bis (4-butylanilino) -5,8-dihydroxyanthraquinone, 4 '-(4-hydroxy-1-anthraquinonylamino) -acetanilide, 1,4-bis [(2,6-diethyl-4-methylphenyl) amino] anthraquinone, 1,4-bis ( Butylamino) -9,10-anthracenedione, 1,4-bis (4-butylanilino) -5,8-dihydroxyanthraquinone, 1,5-bis [(3-methylphenyl) amino] -9 , 10-anthracene On, 1,5-dicyclohexylaminoanthraquinone, 1,4-bis (isopropylamino) anthraquinone, 1,4-bis (methylamino) anthraquinone, 1,4-bis (2,6-diethyl 4-methylanilino) anthraquinone, 2,2 '-(9,10-dioxoanthracene-1,4-diyldiimino) bis (5-methylsulfonate), 1-anilino-4-hydro Roxyantraquinone, 1-hydroxy-4-[(4-methylphenyl) amino] -9,10-anthracenedione, 1,4-bis (para-tolylamino) anthraquinone, 1-amino-4-fetylamino Anthraquinone, N- [4-[(4-hydroxy-anthraquino-1-yl) amino] phenyl] acetamide, 1- (methylamino) -4- (4-methylanilino) anthracene-9,10 -Dione and 1,4,5,8-tetrahydroxyanthraquinone.

In addition to the dispersing aid, it may further comprise a commercially available dispersing aid. Specifically, the SOLSPERSE-5000, SOLSPERSE-12000, SOLSPERSE-22000 of Lubrizol, BYK-SYNERGIST 2100, BYK-SINERGIST 2105, BASF EFKA-6745 or EFKA-6750, etc. may be mentioned.

The dispersing aid comprises 1 to 30 parts by weight based on 100 parts by weight of the pigment in the colorant. When the dispersing aid exceeds 30 parts by weight, the color inherent in the colorant (A) may be altered, and may be discolored by hard baking during the manufacturing process of the colored layer.

(a4) Dispersion solvent

The dispersion solvent is not particularly limited and various organic solvents used in the art may be used.

Specifically, for example, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether Diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate , Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, methyl ethyl Ketone, ace Ketones such as methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3-methoxy Ester, such as methyl propionate, Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned. Preferably, alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate can be used, and more preferably propylene glycol monomethyl ether acetate and propylene glycol mono Ethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like can be used.

The said dispersion solvent can be used individually or in mixture of 2 or more types, respectively.

The dispersion solvent is included 60 to 90% by weight, preferably 70 to 85% by weight based on the total weight of the pigment dispersion composition. Outside the above range may cause a disadvantage in that the storage stability of the pigment dispersion composition is poor.

(a5) dispersion resin

The dispersion resin may be selectively added to act as a dispersion medium of the colorant (A), and the mixture of the dispersion resin (a5) may be used to prepare a better pigment dispersion composition than the use of the dispersion agent (a2) alone. In the case of the dispersion resin, it can be used without limitation as long as it can function as a dispersion medium, but it is preferable to have an acid value in order to have solubility in an alkaline developer in consideration of the developability of the colored photosensitive resin composition prepared from the pigment dispersion composition.

The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be determined by titration using an aqueous potassium hydroxide solution.

In the case of the acid-containing dispersion resin, the compound (b1) having an unsaturated bond with the carboxyl group and the compound (b2) having an unsaturated bond copolymerizable with the compound (b1) may be prepared by copolymerizing.

Specific examples of the compound (b1) having a carboxylic acid group and an unsaturated bond include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of the dicarboxylic acids; mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and the like, and acrylic acid and methacrylic acid are preferred. In the present invention, (meth) acrylate refers to acrylate, methacrylate or both.

The compound illustrated by the said compound (b1) can be used individually or in combination of 2 or more types, respectively. Compound (b2) having an unsaturated bond copolymerizable with the compound (b1) may be, for example, styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p -Methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether or p-vinylbenzyl glycid Aromatic vinyl compounds such as dil ether; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate or t-butyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decane-8-yl (meth) acrylate, 2- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate or isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate or benzyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide compounds such as -methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; Unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane or 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. Unsaturated oxetane compounds, and the like, but are not limited thereto.

The compound illustrated by the said compound (b2) can be used individually or in combination of 2 types or more, respectively.

The dispersion resin is included in an amount of 5 to 60 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the pigment solids in the colorant. When the dispersion resin exceeds 60 parts by weight, the viscosity may be increased by the dispersion resin, and when the dispersion resin is less than 5 parts by weight, the amount of the dispersion resin is insufficient to obtain an atomized pigment dispersion composition.

(a6) dye

The dye may be used without limitation so long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye having solubility in an organic solvent and ensuring reliability such as solubility in an alkaline developer, heat resistance and solvent resistance.

The dye may be selected from acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof, and azo, xanthene, and phthalocyanines. Acid dyes and derivatives thereof can also be selected.

Preferably, the dye may be a compound classified as a dye in the color index (Published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (color dyed yarn).

Specific examples of the dye include C.I. As solvent dyes,

C.I. Solvent yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, and 162;

C.I. Solvent red 8, 45, 49, 122, 125 and 130;

C.I. Solvent oranges 2, 7, 11, 15, 26 and 56;

C.I. Solvent blue 35, 37, 59 and 67;

C.I. Green dyes, such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35, etc. are mentioned.

See also C.I. As an acid dye

CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243 and 251;

CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 , 382, 383, 394, 401, 412, 417, 418, 422 and 426;

C.I. acid oranges 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169 and 173;

CI acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103 , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1 , 335 and 340;

C.I. Acid Violet 6B, 7, 9, 17 and 19;

And dyes such as C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109.

Also as a C.I. direct dye

CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138, and 141;

CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 and 250;

C.I. direct oranges 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106 and 107;

CI direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;

C.I. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104;

And dyes such as C.I.Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82.

In addition, C.I. As modanto dye

C.I. Modanto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 and 65;

CI Modanto Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94 and 95;

C.I. modanto orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 and 48;

CI Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83 and 84;

C.I. modanto violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58;

And dyes such as C.I. modanto green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53.

The colorant (A) may be used in combination of one or more pigments or dyes, respectively. In addition, 0.5 to 25% by weight relative to the total weight of solids in the colored photosensitive resin composition of the present invention, preferably 1 to 20% by weight, more preferably 2 to 15% by weight.

Alkali-soluble resin (B)

Alkali-soluble resins can use those known in the art. For example, it is preferable to include one or more of the compounds consisting of the following formulas 4 to 7, wherein the compounds of formulas 4 to 7 are each 3 to 80 mol%, preferably in molar fractions with respect to the total moles of alkali-soluble resin, respectively. May be included in 5 to 70 mol%. When at least one of the compounds of Formulas 4 to 7 is included within the mole fraction range, the sensitivity and adhesion of the colored photosensitive resin composition may be excellent, and thus peeling of the pattern may not occur during the developing process, and solvent resistance may be excellent.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

An alkali-soluble resin having at least one unit selected from the group consisting of Chemical Formulas 4 to 7 may be prepared by polymerizing with a polymerizable compound.

Specific examples of the unsaturated bond copolymerizable with the chemical formulas 4 to 7 of the alkali-soluble resin include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, and p-methoxy Styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like. Aromatic vinyl compounds; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decane-8-yl (meth) acrylate, 2- Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 3,4-epoxytricyclodecane-8-yl (meth) acrylate, 3,4-epoxytricyclodecane-9-yl Alicyclic (meth) acrylates such as (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide compounds such as -methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; (meth) acrylamide, Unsaturated amide compounds such as N, N-dimethyl (meth) acrylamide; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. And unsaturated oxetane compounds.

The compounds exemplified above may be used alone or in combination of two or more thereof.

In addition, other examples of alkali-soluble resins usable in the present invention include cardo-based resins. The cardo-based resin is, for example, 3,3-bis (4-hydroxyphenyl) -2-benzofuran-1 (3H) -one, 3,3-bis (4-hydroxy-3-methylphenyl)- 2-benzofuran-1 (3H) -one, 3,3-bis (4-hydroxy-2,5-dimethylphenyl) -2-benzofuran-1 (3H) -one, 3,3-bis (4 -Hydroxy-1-naphthyl) -2-benzofuran-1 (3H) -one, 3,3-bis (4-hydroxy-5-isopropyl-2-methylphenyl) -2-benzofuran-1 ( 3H) -one, 3,3-bis (3,5-dibromo-4-hydroxyphenyl) -2-benzofuran-1 (3H) -one, 3,3-bis (4-hydroxy-3 , 5-Diiodinephenyl) -2-benzofuran-1 (3H) -one, 9,9-bis (4-hydroxyphenyl) -10-anthrone, 1,2-bis (4-carboxyphenyl) carbo Column, 1,7-bis (4-carboxyphenyl) carbonan, 2-bis (4-carboxyphenyl) -N-phenylphthalimidine, 3,3-bis (4'-carboxyphenyl) phthalide, 9, 10-bis- (4-aminophenyl) -anthracene, antron dianiline, aniline phthalein, etc. are mentioned. Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone and bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) Hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane and bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxy Phenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane and bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorofetyl) methane and bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2 -Bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3- Methylphenyl) propane and 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-di Butylphenyl) ether and bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3- Methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis ( 4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethyl Phenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene and 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene It may be obtained by polymerizing a compound comprising at least one monomer, which is not limited thereto. Commercially available cardo-based resins include WR-101 (Adeka).

The alkali-soluble resin of the present invention may be used by further mixing various known alkali-soluble resins commonly used in the art as needed.

The alkali-soluble resin has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, preferably 5,000 to 50,000. If the weight average molecular weight of the alkali-soluble resin is outside the above range, the film reduction is not prevented at the time of development, causing a problem that the omission of the pattern portion may occur.

The acid value of the alkali-soluble resin is 50 to 150 (KOH mg / g), preferably 60 to 140 (KOH mg / g), more preferably 80 to 135 (KOH mg / g), most preferably Is 80 to 130 (KOH mg / g). When the acid value of the said alkali-soluble resin is 50-150 (KOHmg / g), solubility to a developing solution improves and a residual film rate improves.

The alkali-soluble resin includes 10 to 80% by weight, preferably 10 to 70% by weight based on the total weight of solids in the colored photosensitive resin composition of the present invention. In the above range, the solubility of the developing solution is sufficient, so that pattern formation is easy, and the film reduction of the pixel portion of the exposed portion is prevented at the time of development, so that the non-pixel portion has good omission.

Photopolymerizable Compound (C)

The photopolymerizable compound is not particularly limited as long as it is a compound that can be polymerized by the action of the photopolymerization initiator (D) described later, but is preferably a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, a trifunctional or higher polyfunctional photopolymerizable compound, or the like. Can be mentioned.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl py. Commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nipbon Kayaku), or Biscotti 158 (Osaka Yuki Kagaku High School).

Specific examples of the bifunctional monomers include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like; commercially available products such as Aronix M-210, M-1100, 1200 (Doagosei), KAYARAD HDDA (Nipbon Kayaku), Biscot 260 (Osaka Yuki Kagaku High School), AH-600, AT-600 or UA-306H (Kyoeisha Kagakusa).

Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trimethylolpropane tri (meth) acrylate. , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxysilane Tied dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are commercially available products such as Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD. DPHA-40H (Nippon Kayaku).

Among the photopolymerizable compounds exemplified above, trifunctional or higher functional (meth) acrylates and urethane (meth) acrylates are particularly preferable in terms of excellent polymerizability and improving strength.

Said photopolymerizable compound can be used individually or in combination of 2 or more types, respectively.

The photopolymerizable compound is preferably contained in 5 to 50% by weight, 7 to 48% by weight relative to the total weight of solids in the colored photosensitive resin composition of the present invention. When the photopolymerizable compound is included in the above range, the intensity and smoothness of the pixel portion are good.

Photopolymerization Initiator (D)

As long as it can superpose | polymerize a photopolymerizable compound (C), a photoinitiator can be used without a restriction | limiting in particular.

In particular, the photopolymerization initiator may be an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound, or a thioxanthone compound in view of polymerization characteristics, start efficiency, absorption wavelength, availability, or price. Preference is given to using at least one compound selected from the group consisting of compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1 -One or 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

As said benzophenone type compound, benzophenone, methyl 0- benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3,3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone or 2,4,6-trimethylbenzophenone.

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6 -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine or 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4, The imidazole compound etc. which the phenyl group of a 4'5,5'- tetraphenyl- 1,2'- biimidazole or a 4,4 ', 5,5' position are substituted by the carboalkoxy group are mentioned. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and OXE-01 and OXE-02 manufactured by BASF are typical examples of the commercially available product.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. There is this.

Moreover, photoinitiators other than the photoinitiator mentioned above can also be used within the range which does not impair the effect of this invention. For example, a benzoin type compound, an anthracene type compound, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. have.

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl or titanocene compounds, etc. can be used further as a photoinitiator.

In addition, the photopolymerization initiator may further include a photopolymerization initiation aid (D-1) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition which concerns on this invention can contain a photoinitiation adjuvant (D-1), and can improve a sensitivity and improve productivity.

As the photopolymerization initiation assistant (D-1), for example, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds and organic sulfur compounds having thiol groups can be preferably used.

It is preferable to use an aromatic amine compound as the amine compound, and specifically, aliphatic amine compounds such as triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone ) Or 4,4'-bis (diethylamino) benzophenone can be used.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine or naphthoxyacetic acid, and the like.

Specific examples of the organic sulfur compound having the thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropanetris (3-mergaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl Late), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. are mentioned. Can be.

The photopolymerization initiator may be included in an amount of 0.1 to 10% by weight based on the total weight of solids in the colored photosensitive resin composition based on solids. When included in the above range, the colored photosensitive resin composition may be highly sensitive to shorten the exposure time, thereby improving productivity and maintaining high resolution. In addition, the strength of the pixel portion formed using the composition under the above-described conditions and smoothness on the surface of the pixel portion can be improved.

In addition, when the photopolymerization initiation aid (D-1) is further used, it is preferable to use the same content range as the photopolymerization initiator (D), and when used in the above range, the sensitivity of the colored photosensitive resin composition is increased, The productivity of the colored layer formed using the composition can be provided.

Solvent (E)

As long as the solvent is effective to dissolve the other components included in the colored photosensitive resin composition, the solvent used in the conventional colored photosensitive resin composition can be used without particular limitation, and in particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters Or amides are preferable.

Specifically, the solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, di Ethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, Ethers such as dipropylene glycol dibutyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-meth Methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate or γ-buty Rockactone, etc. And esters thereof.

The solvent is preferably an organic solvent having a boiling point of 100 ° C. to 200 ° C. in terms of coatability and dryness, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalac Tate, 3-ethoxy propionate, methyl 3-methoxypropionate, etc. can be used.

The solvents exemplified above may be used alone or in combination of two or more thereof.

The solvent may be included 40 to 90% by weight, preferably 50 to 85% by weight relative to the total weight of the colored photosensitive resin composition of the present invention. In the said range, when it apply | coats with coating apparatuses, such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes called a die coater), or an inkjet, the applicability | paintability becomes favorable.

< Photocuring Pattern>

The present invention provides a photocuring pattern made of the colored photosensitive resin composition and an image display device including the photocuring pattern.

The photocuring pattern is not particularly limited as long as it is made of a colored photosensitive resin composition, and examples thereof include color filters, black matrices, column spacers, and the like.

The image display device which may include the photocuring pattern may include a liquid crystal display device, an OLED, a flexible display, and the like, but is not limited thereto, and all image display devices known in the art may be illustrated.

A photocuring pattern can be manufactured by apply | coating the coloring photosensitive resin composition of this invention mentioned above on a base material, photocuring and developing, and forming a pattern.

First, after apply | coating a coloring photosensitive resin composition to a board | substrate, heating and drying remove volatile components, such as a solvent, and obtain a smooth coating film.

As a coating method, it can carry out by a spin coat, cast coating method, the roll coating method, the slit and spin coat, the slit coat method, etc., for example. After coating, heating and drying (prebaking) or drying under reduced pressure are carried out to volatilize volatile components such as a solvent. Here, heating temperature is 70-200 degreeC normally, Preferably it is 80-130 degreeC. The coating film thickness after heat drying is about 1-8 micrometers normally. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that the parallel light beam may be irradiated uniformly to the whole exposure part, and the exact alignment of a mask and a board | substrate is performed. When ultraviolet light is irradiated, curing of the site irradiated with ultraviolet light is performed.

G-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm) and the like can be used as the ultraviolet rays. The irradiation amount of ultraviolet rays may be appropriately selected as necessary, and the present invention is not limited thereto. When the coating film after hardening is contacted with a developing solution and the non-exposed part is melted and developed, the target pattern shape can be formed.

The developing method may be any of a liquid addition method, a dipping method, a spray method and the like. In addition, during development, the substrate may be tilted at an arbitrary angle. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate And sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine and the like.

These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.

The surfactant in the alkaline developer may be at least one selected from the group consisting of nonionic surfactants, anionic surfactants or cationic surfactants.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Specific examples of the anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts. These surfactant can be used individually or in combination of 2 or more types, respectively.

The concentration of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight. After image development, it is washed with water and also 10-60 minutes post-baking may be performed at 150-230 degreeC as needed.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.

Example

A colored photosensitive resin composition was prepared with the components and contents shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 coloring agent V29 0.80 - - 0.40 3.20 - - V31 - 0.80 - - - - - V37 - - 0.80 0.40 - - - V23 - - - - - - 0.80 B15: 6 1.92 1.92 1.92 1.92 1.92 2.72 2.72 R177 3.68 3.68 3.68 3.68 1.28 3.68 3.68 CB 1.60 1.60 1.60 1.60 1.60 1.60 1.60 Alkali-soluble resin (B) 6.50 6.50 6.50 6.50 6.50 6.80 6.50 Photopolymerizable Compound (C) 2.79 2.79 2.79 2.79 2.79 2.92 2.79 Photopolymerization Initiator (D) 0.56 0.56 0.56 0.56 0.56 0.58 0.56 additive F-1 0.02 0.02 0.02 0.02 0.02 0.02 0.02 F-2 2.13 2.13 2.13 2.13 2.13 1.68 2.13 Solvent (E) E-1 3.00 3.00 3.00 3.00 3.00 3.00 3.00 E-2 77.00 77.00 77.00 77.00 77.00 77.00 77.00 CB: Carbon-black (MA-8, manufactured by Mitsubishi Corporation)
V29: pigment violet 29 (Luprofil Violet 50-1105 C4, manufactured by Basf)
V31: Pigment Violet 31 (AP Violet 1, manufactured by AP-Color)
V37: Pigment Violet 37 (Cromophtal Violet B, manufactured by Ciba)
V23: pigment violet 23 (Fastogen Super Violet RN-F, manufactured by DIC Corporation)
R177: Pigment Red 177 (ATY-TR, manufactured by DIC Corporation)
B15: 6: Pigment Blue 15: 6 (EP-193, manufactured by DIC Corporation)
B: cardo resin (WR-101, Adeka)
C: dipentaerythritol hexaacrylate (Kayarad DPHA: manufactured by Nippon Kayaku Co., Ltd.)
D: 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone-1- (O-acetyloxime) (Irgacure OXE-02: manufactured by BASF Corporation)
E-1: n-butanol
E-2: Propylene Glycol Monomethyl Ether Acetate
F-1: Solsper's 5000 (manufactured by Lubrisol)
F-2: DiperBYK-163 (by BYK Corporation)

Experimental Example

A glass substrate of 5 cm x 5 cm (Corning # 1737) was washed with a neutral detergent and water and dried. The glass substrate was spin-coated so that the final film thickness was 3.0 µm, and dried for 1 to 2 minutes after pre-firing at 80 to 120 ° C to remove the solvent. Thereafter, a ² cm × ² cm pattern is formed by exposing at an exposure dose of 40 to 100 mJ / cm ^2, and the non-exposed part is removed using an alkaline aqueous solution. Subsequently, the substrate was post-fired at 200 to 250 ° C. for 10 to 30 minutes to prepare a patterned substrate.

One. Color change (ΔE ab ) Measure

After putting the produced colored pattern board | substrate further in the post-baking process (200-250 degreeC) for 2 hours, the color change before and after 2 hours was measured. Color change was measured using a colorimeter OSP-SP2000 (Olympus), the results are shown in Table 2.

2. Residual rate Measure

After putting the produced colored pattern board | substrate further in the post-baking process (200-250 degreeC) for 2 hours, the film thickness before and after 2 hours was measured. The film thickness was measured using a film thickness meter (Dektak6M (Veec)), and the change rate of the film thickness is shown in Table 2.

3. optical density ( optical density ) Measure

The produced colored pattern board | substrate was measured using the optical density (OD) measuring machine (X-rite 301 Densitometer), and the result in 3 micrometers which is the final film thickness is shown in Table 2.

Item Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Color change 1.2 1.1 1.2 1.2 1.8 2.1 2.2 Residual rate 1.4% 1.3% 1.4% 1.4% 2.5% 4.5% 4.9% Optical density 4.09 3.98 4.03 3.97 3.56 3.61 3.52

Referring to Table 2, it can be seen that the embodiments of the present invention have a smaller color change and a significantly smaller change rate of the film thickness (higher residual film rate) than the comparative example. In addition, it can be seen that the optical density measurement results are higher than those of the comparative examples in the examples.

On the other hand, in the case of Example 5 in which the content of the pigment violet pigment according to the present invention was added in an excessive amount, it was confirmed that the optical density decreased slightly.

Claims

(A) a coloring agent, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photoinitiator, and (E) solvent,
The colorant (A) includes a black pigment and an organic pigment containing a pigment violet pigment,
The pigment violet pigment is composed of at least one selected from pigment violet 29, pigment violet 31 and pigment violet 37,
The organic pigment is 30 to 80% by weight, and the black pigment is 20 to 70% by weight based on the total weight of the colorant solids, coloring photosensitive resin composition.

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The colored photosensitive resin composition according to claim 1, wherein at least one selected from the group consisting of the pigment violet 29, the pigment violet 31, and the pigment violet 37 is contained in an amount of 10 to 40% by weight based on the total weight of the organic pigment. .

The coloring photosensitive resin composition of Claim 1 in which the said organic pigment further contains Pigment Blue 15: 6.

The coloring photosensitive resin composition of Claim 1 whose said black pigment is carbon black.

The photocuring pattern manufactured from the coloring photosensitive resin composition of any one of Claims 1 and 3-5.

The photocuring pattern of claim 6, wherein the photocuring pattern is at least one selected from the group consisting of a color filter, a black matrix, and a column spacer.

An image display device comprising the photocuring pattern of claim 6.