KR102508343B1 - A colored photo sensitive resin composition, a color filter comprising the same, and a display devide comprising the color filter - Google Patents

Abstract

The present invention provides a colored photosensitive resin composition capable of pattern formation without a pre-bake process, (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator and ( E) includes a solvent, wherein the (E) solvent is at least one of MMB (3-methoxy-3-methyl-1-butanol) and MMB-Ac (3-methoxy-3-methyl-1-butyl acetate) It provides a colored photosensitive resin composition characterized in that it comprises, a color filter manufactured using the same, and a display device including the color filter.

Description

Colored photosensitive resin composition, a color filter manufactured using the same, and a display device including the color filter

The present invention relates to a colored photosensitive resin composition, a color filter manufactured using the same, and a display device including the color filter.

BACKGROUND OF THE INVENTION Color filters are widely used in imaging devices and various display devices such as liquid crystal display devices (LCDs), and their application range is rapidly expanding. A color filter used in a liquid crystal display device or an imaging device is usually coated uniformly with a colored photosensitive resin composition containing colorants corresponding to each of red, green, and blue colors on a substrate on which a black matrix is patterned by spin coating, An operation of exposing and developing a coating film formed by heating and drying (hereinafter sometimes referred to as pre-baking) and, if necessary, further heating and curing (hereinafter sometimes referred to as post-baking) is repeated for each color to create pixels of each color. It is manufactured by forming. At this time, immediately after application, a VD (Vacuum Dry) process, which is a solvent removal process of the resist, and a pre-bake process for completely removing the remaining solvent are performed.

As one of the major current CF (Color Filter) substrate manufacturing methods, color resist is coated in a slit coating method. Productivity is increased by shortening the tact time. However, surface defects such as VD stains occur due to rapid drying of the resist due to the reduced pressure of the high vacuum. Therefore, there is a demand for a highly sensitive colored photosensitive resin composition capable of forming a uniform coating film even when a high vacuum pressure is reduced.

As a way to solve this problem, a method of suppressing VD staining by using a high boiling point solvent can be used, but as the evaporation rate of the solvent is slow, the VD tact time increases.

In addition, in recent years, pixels with high color density are required, and the content of pigment and carbon black used in the colored photosensitive resin composition is increasing, resulting in poor fluidity during drying and increasing VD stains.

Korean Patent Publication No. 10-2016-0112615 is an invention related to a colored photosensitive resin composition, and discloses a technology for improving the coating properties and compatibility of a liquid crystal display by suppressing the occurrence of VD stains and PIN stains, but pre-baking (Pre-bake) process time increase and the resulting reduction in productivity and adhesion problems are not being solved.

Republic of Korea Patent Publication No. 10-2016-0112615

The present invention is to improve the above-mentioned problems of the prior art, to provide a colored photosensitive resin composition in which all solvents are volatilized without residual solvent without a pre-bake process, preventing the occurrence of VD stains, and having improved adhesion. aims to do

In addition, an object of the present invention is to provide a color filter including a colored pattern prepared using the colored photosensitive resin composition and a display device including the color filter.

In order to achieve the above object, the present invention, in the colored photosensitive resin composition capable of pattern formation without a pre-bake process, (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound , (D) a photopolymerization initiator and (E) a solvent, wherein the (E) solvent is MMB (3-methoxy-3-methyl-1-butanol) and MMB-Ac (3-methoxy-3-methyl-1- butyl acetate) to provide a colored photosensitive resin composition comprising at least one.

In addition, the present invention provides a method for forming a colored pattern using the colored photosensitive resin composition.

In addition, the present invention provides a color filter comprising a colored pattern made of the colored photosensitive resin composition.

In addition, the present invention provides a display device including the color filter.

The colored photosensitive resin composition of the present invention includes at least one of MMB (3-methoxy-3-methyl-1-butanol) and MMB-Ac (3-methoxy-3-methyl-1-butyl acetate) as a solvent, The solvent is completely volatilized without residual solvent even without a pre-bake process, thereby preventing the occurrence of VD stains and providing a colored photosensitive resin composition with improved adhesion.

In addition, when forming a colored pattern using the colored photosensitive resin composition, the process time is shortened according to the omission of the pre-bake process, thereby providing an effect of improving productivity.

In addition, a color filter manufactured using the colored photosensitive resin composition and a display device including the color filter provide excellent characteristics in terms of drivability and durability.

1 is a flowchart showing a method of forming a colored pattern using a colored photosensitive resin composition according to the present invention.
2 to 5 are diagrams illustrating criteria for determining adhesion of colored patterns in Experimental Example 2 of the present invention.

The present invention provides a colored photosensitive resin composition capable of pattern formation without a pre-bake process, (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator and ( E) includes a solvent, wherein the (E) solvent is at least one of MMB (3-methoxy-3-methyl-1-butanol) and MMB-Ac (3-methoxy-3-methyl-1-butyl acetate) It provides a colored photosensitive resin composition characterized in that it comprises, a color filter manufactured using the same, and a display device including the color filter.

The colored photosensitive resin composition according to the present invention contains at least one of MMB and MMB-Ac as a solvent, so that even when a pattern is formed without a pre-bake process, all solvents are volatilized without remaining solvent, so that the pattern is not peeled off. A uniform pattern can be formed. Accordingly, the process time can be shortened, and productivity can be improved.

<Colored photosensitive resin composition>

Hereinafter, each component constituting the colored photosensitive resin composition of the present invention will be described in detail. However, the present invention is not limited by these components.

(A) colorant

As the colorant, one or more of pigments and dyes commonly used in the art may be used, if necessary, and any colorant known in the art may be used without limitation.

The pigment includes organic pigments and inorganic pigments, and, if necessary, resin treatment, surface treatment using a pigment derivative having an acidic or basic group introduced, graft treatment of the pigment surface by a polymer compound, etc., atomization by a sulfuric acid atomization method, etc. treatment, a washing treatment with an organic solvent or water for removing impurities, or a treatment for removing ionic impurities by an ion exchange method or the like may be performed.

As the organic pigment, various pigments used in printing ink, inkjet ink, etc. may be used. Specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, Perylene Pigment, Perinone Pigment, Dioxazine Pigment, Anthraquinone Pigment, Dianthraquinonyl Pigment, Anthrapyrimidine Pigment, Ananthrone Pigment, Indanthrone Pigment, Pravanthrone Pigment, Pyranthrone Pigment, Diketopyrororopyrrole Pigment etc. can be mentioned.

In addition, as the inorganic pigment, metal compounds such as metal oxides and metal complex salts may be used. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, organic oxides of metals or composite metal oxides, such as black pigments, titanium black, and pigments that produce black by mixing red, green, and blue colors; and the like.

In particular, the organic and inorganic pigments include compounds classified as pigments in color index (published by The Society of Dyers and Colourists), more specifically, the following color index (C.I.) numbers Although a pigment can be mentioned, it is not necessarily limited to these.

C.I. Pigment Yellow 13, 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, 179, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264;

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;

C.I. Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 16, 21, 28, 60, 64 and 76;

C.I. Pigment Green 7, 10, 15, 25, 36, 47, 58 and 59;

C.I Pigment Brown 28;

C.I Pigment Black 1 and 7;

As the pigment, it is preferable to use a pigment dispersion in which the particle size of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle size of the pigment include a method of dispersing treatment by containing a pigment dispersant, and according to the method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

The pigment dispersant is added for deagglomeration and stability of the pigment, and those commonly used in the art may be used without limitation. Specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, Surfactants, such as a polyester type and a polyamine type, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.

Specific examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.

Specific examples of the anionic surfactant 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 dodecylbenzenesulfonate and Alkylaryl sulfonic acid salts, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

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, etc. are mentioned.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines may be mentioned. there is.

In addition, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). Commercial products of the acrylate-based dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150, and the acrylate-based dispersant may be used alone or in combination of two or more. can

As the pigment dispersant, other resin-type pigment dispersants may be used in addition to the acrylate-based dispersant. The other resin-type pigment dispersants include known resin-type pigment dispersants, particularly polycarboxylic acid esters represented by polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, and (partial) polycarboxylic acids. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) an oily dispersant such as an amide formed by reaction of a polyester having a carboxyl group with a poly(lower alkyleneimine) or a salt thereof; water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; modified polyacrylate; adducts of ethylene oxide/propylene oxide; and phosphate esters.

Commercially available products of the other resin-type pigment dispersants include, for example, BYK (Big) Chemistry trade names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER as cationic resin dispersants. BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF brand names: 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 of Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Trade names of Kawaken Fine Chemical Co.: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Trade names of Ajinomoto: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Trade names of Kyoeisha Chemical Co., Ltd.: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44 and the like.

In addition to the above acrylate-based dispersants, other resin-type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylate-based dispersant.

The pigment dispersant may be included in an amount of 5 to 60% by weight, preferably 15 to 50% by weight, based on 100% by weight of the solid content of the pigment. When the pigment dispersant is included within the above range, it is possible to maintain an appropriate viscosity level that is easy to prepare the colored photosensitive resin composition, and it is preferable that the gelation process is easy after atomization and dispersion of the pigment.

The dye may be used without limitation as long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye capable of securing reliability such as solubility in an alkali developing solution, heat resistance, and solvent resistance while having solubility in organic solvents.

As the dye, acid dyes having an acid group such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof may be used. Acid dyes of the system and their derivatives may also be selected. Preferably, the dyes include compounds classified as dyes in the color index (published by The Society of Dyers and Colourists) or known dyes described in dyeing notes (dyed yarns).

Specific examples of the dye include,

C.I. As a solvent dye,

C.I. yellow dyes such as Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163;

C.I. red dyes such as Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;

C.I. orange dyes such as Solvent Orange 2, 7, 11, 15, 26, 41, 45, 56, 62;

C.I. blue dyes such as Solvent Blue 5, 35, 36, 37, 44, 59, 67, and 70;

C.I. violet dyes such as Solvent Violet 8, 9, 13, 14, 36, 37, 47, 49;

C.I. green dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35;

C.I. Among solvent dyes, C.I. Solvent Yellow 14, 16, 21, 56, 151, 79, 93; are preferred and dual C.I. Solvent Yellow 21, 79; is more preferred.

Also, C.I. As an acid dye,

C.I. 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, 251, etc. ;

C.I. 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, 88 217 ,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, 426 and the like red dyes;

orange dyes such as C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C.I. 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 blue dyes such as , 335 and 340;

violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19, 66;

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

C.I. Among acid dyes, C.I. Acid Yellow 42 having excellent solubility in organic solvents; C.I. Acid Green 27 is more preferred.

Also as a C.I. direct dye,

C.I. 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, yellow dyes such as 141;

C.I. 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, 250;

orange dyes such as C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. 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, 189 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, blue dyes such as 293;

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

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

Also, C.I. As a modanto dye,

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

C.I. 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, red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

C.I. Orange such as Modanto Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 dyes;

C.I. 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, blue dyes such as 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

violet dyes such as C.I. Modanto Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

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

The content of the colorant may be included as 5 to 60% by weight, preferably 10 to 45% by weight based on the total weight of solids in the colored photosensitive resin composition. When the colorant is included within the above range, it is preferable that the color density of the pixels is sufficient when the thin film is formed, and the leakage of non-pixel parts is not reduced during development, so that residues are not easily generated.

In the present invention, the total weight of the solids in the colored photosensitive resin composition means the total weight of the remaining components except for the solvent of the colored photosensitive resin composition.

(B) alkali soluble resin

The alkali-soluble resin is characterized in that it is produced by copolymerization of (b1) an ethylenically unsaturated monomer having a carboxyl group as an essential component in order to be soluble in an alkali developer used in the developing process when forming a pattern.

The content of the alkali-soluble resin may be included as 10 to 80% by weight, preferably 20 to 60% by weight based on the total weight of solids in the colored photosensitive resin composition. When the alkali-soluble resin is included within the above range, the solubility in the developing solution is sufficient to facilitate pattern formation, and film reduction of the pixel portion of the exposed portion is prevented during development, so that the omission of the non-pixel portion becomes good, which is preferable. do.

Preferably, the acid value of the alkali-soluble resin is 30 mgKOH/g to 150 mgKOH/g, and thus compatibility with the dye and stability over time of the colored photosensitive resin composition can be improved. When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, it is difficult to secure a sufficient development rate for the colored photosensitive resin composition, and when it exceeds 150 mgKOH / g, the adhesion with the substrate is reduced and the short circuit of the pattern is likely to occur In addition, a compatibility problem with the dye may cause the dye to precipitate in the colored photosensitive resin composition, or the stability over time of the colored photosensitive resin composition may decrease and the viscosity may increase.

A hydroxyl group may be added to secure additional developability of the alkali-soluble resin. When giving a hydroxyl group to the alkali-soluble resin, there is an effect of improving the development rate.

It is preferable that the sum of the hydroxyl values of the alkali-soluble resin and the photopolymerizable compound is 50 mgKOH/g to 250 mgKOH/g. When the sum of the alkali-soluble resin and the hydroxyl group of the photopolymerizable compound is less than 50 mgKOH/g, a sufficient developing rate cannot be secured, and when it exceeds 250 mgKOH/g, the dimensional stability of the formed pattern is lowered, resulting in Straightness is likely to be poor, and compatibility with the dye is lowered, which may cause a problem of stability over time.

(b1) an ethylenically unsaturated monomer having a carboxyl group

Specific examples of the ethylenically unsaturated monomer having a carboxyl group 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 these dicarboxylic acids; Examples include mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate, and acrylic acid and methacrylic acid are preferable.

The alkali-soluble resin can be prepared by copolymerizing the ethylenically unsaturated monomer having a carboxyl group and the ethylenically unsaturated monomer having a (b2) hydroxyl group. Alternatively, the alkali-soluble resin may be prepared by copolymerizing a copolymer of the ethylenically unsaturated monomer having a carboxyl group with a compound having a (b3) glycidyl group. Alternatively, the alkali-soluble resin may be prepared by copolymerizing the ethylenically unsaturated monomer having the carboxyl group, the ethylenically unsaturated monomer having the hydroxyl group, and the compound having the glycidyl group.

(b2) an ethylenically unsaturated monomer having a hydroxyl group

Specific examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy- There are 3-phenoxypropyl (meth)acrylate, N-hydroxyethyl acrylamide, etc., and 2-hydroxyethyl (meth)acrylate is preferable, and two or more types may be used in combination.

(b3) a compound having a glycidyl group

Specific butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, ethyl glycidyl of the compound having a glycidyl group Dill ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, aryl glycidyl ether, glycidyl methacrylate There are cydyl esters, and butyl glycidyl ether, aryl glycidyl ether, and methacrylic acid glycidyl ester are preferable, and two or more may be used in combination.

The alkali-soluble resin may be prepared by copolymerizing (b4) unsaturated monomers.

(b4) unsaturated monomers

The unsaturated monomers may be used alone or in combination of two or more, and are not limited to the following examples.

Styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethylether, p-vinyl Aromatic vinyl compounds, such as benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m -N-substituted maleimide compounds such as methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-methoxyphenylmaleimide;

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]decan-8-yl(meth)acrylate, 2- alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate;

aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate;

3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. of unsaturated oxetane compounds.

(C) photopolymerizable compound

The photopolymerizable compound is a compound that can be polymerized by the action of light and a photopolymerization initiator (D) described later, and includes monofunctional monomers, bifunctional monomers, and other multifunctional monomers. Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrroly. money, etc. Specific examples of the bifunctional monomer 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, etc. are mentioned. Specific examples of other multifunctional monomers include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and pentaerythritol. Tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaeryth Ritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are mentioned.

Among these, bifunctional or higher functional monomers are preferably used.

The amount of the photopolymerizable compound may be included in an amount of 5 to 50% by weight, preferably 10 to 50% by weight, based on the total weight of solids in the colored photosensitive resin composition. When the photopolymerizable compound is included within the above range, it is preferable because the strength and reliability of the pixel portion become good.

(D) photopolymerization initiator

The photopolymerization initiator is a compound for initiating polymerization of the photopolymerizable compound, and includes oxime-based, acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, benzoin-based, anthraquinone-based, and biimidazole-based compounds alone. Or it may be used in combination of two or more, preferably containing an oxime-based photopolymerization initiator.

The oxime-based photopolymerization initiator preferably contains one or two methyl radicals in one molecule, and most preferably contains two methyl radicals, and thus may have an effect of improving adhesion.

For example, the oxime-based photopolymerization initiator preferably includes at least one of a compound represented by Formula 1 below or a compound represented by Formula 2 below.

[Formula 1]

이고; R₂ 및 R₃은 각각 독립적으로 히드록시기 또는 탄소수 1 내지 8의 알킬기로 치환 또는 비치환된 탄소수 1 내지 8의 알킬기, 페닐기, 벤질기 또는 디페닐설파이드기이며; R₄는 탄소수 1 내지 4의 알킬렌기이고; R₅는 탄소수 3 내지 8의 시클로알킬기이다.In Formula 1, R ₁ is

ego; R ₂ and R ₃ are each independently an alkyl group having 1 to 8 carbon atoms unsubstituted or substituted with a hydroxyl group or an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group or a diphenylsulfide group; R ₄ is an alkylene group having 1 to 4 carbon atoms; R ₅ is a cycloalkyl group having 3 to 8 carbon atoms.

[Formula 2]

In Formula 2, R ₆ and R ₇ are each independently a C1 to C20 linear or branched alkyl group, a C3 to C20 cycloalkyl group, a C4 to C20 cycloalkylalkyl group, a C4 to C20 alkylcycloalkyl group, a C3 to C20 A heteroaryl group or a C6 to C20 aryl group, and hydrogen contained in the alkyl group, cycloalkyl group, cycloalkylalkyl group, alkylcycloalkyl group, heteroaryl group or aryl group is independently a halogen, a phenyl group, a nitro group, a hydroxy group , It is substituted or unsubstituted with one or more groups selected from the group consisting of a carboxyl group, a sulfonic acid group, an amino group, a cyano group and an alkoxy group, X and Y are each independently hydrogen, a C1 to C20 linear or branched alkyl group, C3 to C20 A cycloalkyl group, a C4 to C20 cycloalkylalkyl group, a C4 to C20 alkylcycloalkyl group, or a C7 to C20 aralkyl group, wherein hydrogen contained in the alkyl group, cycloalkyl group, cycloalkylalkyl group, alkylcycloalkyl group or aralkyl group is independently is unsubstituted or substituted with one or more groups selected from the group consisting of a halogen, a nitro group, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group, a cyano group and an alkoxy group, and M is substituted or unsubstituted with a C1 to C5 linear alkyl group. is a group derived from carbazole, fluorene, dibenzofuran or dibenzothiophene.

Specifically, the compound represented by Formula 1 may include a compound represented by Formula 3 below, and the compound represented by Formula 2 may include a compound represented by Formula 4 below.

[Formula 3]

[Formula 4]

The acetophenone-based photopolymerization initiator includes diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyl) Ethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2 Oligomer of -benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propan-1-one and the like, and among these, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one can be particularly preferably used.

The benzophenone-based photopolymerization initiator includes benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4' -Bis(diethylamino) benzophenone etc. are mentioned.

The triazine-based photopolymerization initiator includes 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'- Dimethoxy styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tril)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho 1-yl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy naphtho 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloro methyl(piperonyl)-6-triazine, 2,4-trichloromethyl(4'-methoxystyryl)-6-triazine, and the like.

Examples of the thioxanthone-based photopolymerization initiator include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. can

Examples of the benzoin-based photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethylketal.

Examples of the anthraquinone-based photopolymerization initiator include 2-ethyl anthraquinone, octamethyl anthraquinone, 1,2-benz anthraquinone, and 2,3-diphenyl anthraquinone.

The biimidazole-based photopolymerization initiator includes 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, the phenyl group at the 4,4', 5,5' position is carboalkoxy The imidazole compound etc. which are substituted by the group are mentioned.

The photopolymerization initiator may be included in an amount of 0.5 to 6% by weight based on the total solid content of the colored photosensitive resin composition, and is more preferably included in an amount of 1.5 to 4.5% by weight. This content range takes into account the photopolymerization rate of the photopolymerizable compound and the physical properties of the final coating film. If it is less than the above range, the polymerization rate is low and the overall process time may be lengthened. Conversely, if it exceeds the above range, crosslinking reaction may occur due to excessive reaction Over time, the physical properties of the coating film may rather deteriorate. When the photopolymerization initiator is used within the above content range, strength of the pixel portion and linearity of the pattern may be improved.

The photopolymerization initiator may be used in combination with a photopolymerization initiation aid. When a photopolymerization initiation auxiliary is used in combination with the photopolymerization initiator, the colored photosensitive resin composition containing them becomes more sensitive and productivity is improved when forming a support spacer for maintaining a cell gap using the photopolymerization initiator, which is preferable.

The photopolymerization initiation aid may be used to increase polymerization efficiency, and at least one compound selected from the group consisting of amine-based compounds, alkoxyanthracene-based compounds, thioxanthone-based compounds, carboxylic acids and sulfonic acid compounds may be used, preferably Preferably, it may be selected from the group consisting of carboxylic acid and sulfonic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, -2-dimethylaminoethyl benzoate, 4 -Dimethylaminobenzoic acid, 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzphenone (common name, Michler's ketone), 4,4'-bis(diethylamino)benzo phenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. are mentioned, and among these, 4,4'-bis(diethylamino)benzophenone is preferable.

Examples of the alkoxyanthracene-based compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. can

As the thioxanthone-based compound, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-pro A foxy thioxanthone etc. are mentioned.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichloro and aromatic heteroacetic acids such as phenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The photopolymerization initiation aid may be prepared directly or purchased commercially.

The photopolymerization initiation aid is usually 10 moles or less, preferably used within the range of 0.01 to 5 moles per mole of the photopolymerization initiator. When the photopolymerization initiation aid is used within the above range, an effect of improving productivity can be expected by increasing the polymerization efficiency.

(E) solvent

The solvent is characterized in that it contains at least one of MMB (3-methoxy-3-methyl-1-butanol) and MMB-Ac (3-methoxy-3-methyl-1-butyl acetate). At least one of MMB and MMB-Ac is preferably included in an amount of 1 to 20% by weight based on the total weight of the solvent.

Specifically, when the solvent includes MMB, a uniform pattern can be formed without peeling of the pattern due to excellent adhesion, and when the solvent includes MMB-Ac, a solvent commonly used in the art (eg For example, it has a lower boiling point than propylene glycol monomethyl ether acetate), so even when patterns are formed without a pre-bake process, all solvents are volatilized without remaining solvent, leaving no VD (Vacuum Dry) stains. may not be Accordingly, process time may be shortened and productivity may be improved. Therefore, it may be more preferable to include both 3-methoxy-3-methyl-1-butanol (MMB) and 3-methoxy-3-methyl-1-butyl acetate (MMB-Ac) as the solvent.

In addition to MMB and MMB-Ac, as long as the solvent is effective in dissolving other components included in the colored photosensitive resin composition, the solvent used in the colored photosensitive resin composition may be further included without particular limitation, and ethers and aromatics may be used. Examples include hydrocarbons, ketones, alcohols, esters or amides.

Examples of solvents that may be further included in the solvent other than MMB and MMB-Ac include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene such as methyl cellosolve acetate and ethyl cellosolve acetate Alkylene glycol alkyl ether acetates such as glycol alkyl ether acetates, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, benzene, toluene, Aromatic hydrocarbons such as xylene and mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, etc. alcohols, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone.

The solvent is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C in terms of coating and drying properties, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalac tate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like can be used.

The solvent may be included in an amount of 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition of the present invention. When the solvent is included within the above content range, the effect of improving the coating property when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), an inkjet, or the like It is desirable because it provides

(F) additives

The colored photosensitive resin composition according to the present invention may further include additives as needed, and as specific examples, at least one selected from other polymer compounds, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and aggregation inhibitors may be used. .

Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, and polyurethanes. can be heard

The surfactant may be used to further improve the film formation of the photosensitive resin composition, and a fluorine-based surfactant or a silicone-based surfactant may be preferably used.

The silicone-based surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, SH8400 from Dow Corning Toray Silicon as commercial products, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, and TSF-4460 from GE Toshiba Silicone. , TSF-4452, etc. Examples of the fluorine-based surfactant include Megapiece F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink and Chemicals Co., Ltd. as commercial products. The surfactants exemplified above may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-( 3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethyne Toxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned. Adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be included in a weight fraction of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the solid content of the colored photosensitive resin composition.

Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.

Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyriazole, alkoxybenzophenone, and the like.

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

< Method of forming color pattern, color filter including the color pattern, and display device including the color filter >

The present invention also provides a method for forming a colored pattern using the colored photosensitive resin composition according to the present invention, a color filter including the colored pattern, and a display device including the color filter.

Referring to Figure 1, the method of forming the colored pattern, the step of applying a colored photosensitive resin composition on a substrate; vacuum drying the substrate coated with the colored photosensitive resin; exposing the substrate dried under reduced pressure; developing the exposed substrate; and post-baking the developed substrate, and is characterized in that it does not include a pre-bake process.

First, as a method of applying the colored photosensitive resin composition on a substrate, for example, spin coating, casting coating, roll coating, slit and spin coating, or slit coating may be used, and the substrate is particularly limited. It may be, for example, glass, silicon (Si), silicon oxide (SiOx) or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

Next, the step of drying the substrate coated with the colored photosensitive resin under reduced pressure may be performed by putting the substrate into a reduced pressure chamber and drying the substrate under reduced pressure at a pressure of 60 to 100 Pa, and thus the colored photosensitive resin. The solvent containing may be removed.

In the case of the prior art, the colored photosensitive resin composition is usually applied on a substrate, dried under reduced pressure, and then heat-dried through pre-bake, but the colored photosensitive resin composition according to the present invention is used. In the case of forming a colored pattern by using the pre-bake process, the pre-bake process can be omitted because all solvents are volatilized without remaining solvent. Accordingly, even if the pre-bake process is omitted, a uniform pattern may be formed without peeling of the pattern, process time may be shortened, and productivity may be improved.

The coating film obtained in this way is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel light rays are uniformly irradiated to the entire exposure area and accurate positioning of the mask and the substrate is performed. When irradiated with ultraviolet rays, the portion irradiated with ultraviolet rays is cured.

As the ultraviolet rays, g-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm), and the like may be used. The irradiation amount of ultraviolet rays can be appropriately selected as needed, and is not limited thereto in the present invention. When the cured coating film is contacted with a developing solution to dissolve the unexposed portion and develop, a desired pattern shape can be formed.

As the developing method, any of a liquid addition method, a dipping method, a spray method, and the like may be used. Further, the substrate may be tilted at an arbitrary angle during development. The developing solution is usually an aqueous solution containing an alkaline compound and a surfactant. Any of inorganic and organic alkaline compounds may be sufficient as the said alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Further, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, etc. are mentioned.

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

As the surfactant in the alkali developer, at least one selected from the group consisting of nonionic surfactants, anionic surfactants, and cationic surfactants may be used.

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, and polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate or sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate, dodecylbenzenesulfonic acid Alkylaryl sulfonic acid salts, such as sodium and sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride or lauryltrimethylammonium chloride. These surfactants can be used alone or in combination of two or more.

The concentration of the surfactant in the developing solution is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass. After development, it is washed with water and, if necessary, post-baked at 150 to 230°C for 10 to 60 minutes.

The display device including the color filter may include a liquid crystal display device, an OLED, a flexible display, and the like, but is not limited thereto, and all applicable display devices known in the art may be exemplified.

Hereinafter, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are only examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention has been indicated in the claims, and furthermore contains all changes within the meaning and range equivalent to the written claims. In the following Examples and Comparative Examples, "%" and "parts" indicating content are based on mass unless otherwise specified.

Preparation Example 1: Colorant Dispersion Composition

As a pigment, C.I. 12.5 parts by weight of Pigment Blue 15:6, 7.5 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, C.I. 1.2 parts by weight of Acid Red 52, 72 parts by weight of propylene glycol methyl ether acetate and 8 parts by weight of propylene glycol monomethyl ether as a solvent were mixed and dispersed in a bead mill for 12 hours to prepare a colorant dispersion composition.

Synthesis Example 1: Synthesis of alkali-soluble resin

100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN, 23.0 parts of 2-ethylhexyl acrylate, 4 - 1.6 parts of methyl styrene, 46.0 parts of glycidyl methacrylate, and 3 parts of n-dodecyl mercapto were added, and after nitrogen substitution, the temperature of the reaction solution was raised to 80° C. while stirring, and reacted for 4 hours. Subsequently, the temperature of the reaction solution was lowered to room temperature, nitrogen in the flask was replaced with air again, 0.2 part of triethylamine, 0.1 part of 4-methoxy phenol, and 23.3 parts of acrylic acid were added, and the mixture was reacted at 100° C. for 6 hours. Thereafter, after lowering the temperature of the reaction solution to room temperature, adding 6.0 parts of succinic anhydride, and reacting at 80° C. for 6 hours, an alkali-soluble resin of Synthesis Example 1 was synthesized.

The alkali-soluble resin of Synthesis Example 1 has a solid acid value of 32.8 mgKOH/g, a weight average molecular weight of about 6350 as measured by GPC, and a glass transition temperature of -12°C as measured by differential scanning calorimetry.

Preparation of colored photosensitive resin compositions according to Examples and Comparative Examples

Referring to Table 1 below, colored photosensitive resin compositions according to Examples and Comparative Examples were prepared.

(Unit: g) (A) (B) (C) (D-1) (D-2) (E-1) (E-2) (E-3) (E-4) Example 1 21.9 11.8 5.4 0.5 60.2 Example 2 21.9 11.8 5.4 0.5 60.2 Example 3 21.9 11.8 5.4 0.5 4.2 56 Example 4 21.9 11.8 5.4 0.5 60.2 Example 5 21.9 11.8 5.4 0.5 60.2 Example 6 21.9 11.8 5.4 0.5 4.2 56 Example 7 21.9 11.8 5.4 0.5 4.2 56 Example 8 21.9 11.8 5.4 0.5 4.2 56 Comparative Example 1 21.9 11.8 5.4 0.5 60.2 Comparative Example 2 21.9 11.8 5.4 0.5 4.2 60.2 Comparative Example 3 21.9 11.8 5.4 0.5 60.2 Comparative Example 4 21.9 11.8 5.4 0.5 4.2 60.2

(A) colorant: Preparation Example 1

(B) Alkali-soluble resin: Synthesis Example 1

(C) photopolymerizable compound: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., Japan)

(D-1) photopolymerization initiator: a compound represented by the following formula (3)

[Formula 3]

(D-2) photopolymerization initiator: a compound represented by the following formula (4)

[Formula 4]

(E-1) solvent: MMB (3-methoxy-3-methyl-1-butanol, boiling point 174 ° C)

(E-2) Solvent: MMB-Ac (3-methoxy-3-methyl-1-butyl acetate, boiling point 68 ° C)

(E-3) Solvent: PGDA (propylene glycol diacetate, boiling point 191 ℃)

(E-4) Solvent: PGMEA (propylene glycol monomethyl ether acetate, boiling point 145 ℃)

Experimental Example 1: Evaluation of VD stains according to drying speed under reduced pressure

The colored photosensitive resin composition prepared according to the above Examples and Comparative Examples was applied on a glass substrate by spin coating, and then vacuum dried to form a thin film so that the vacuum degree was 65 Pa, and the time to reach 65 Pa was measured and evaluated according to the criteria below, and the results are shown as VD TIME in Table 2 below.

The thin film thus prepared was photographed with an optical microscope, and the number of VD stains occurring within a 1 cm x 1 cm area was counted and evaluated according to the criteria below, and the results are shown in Table 2 below.

<VD TIME Evaluation Criteria>

◎: 20 seconds or more to less than 25 seconds

○: 25 seconds or more to less than 30 seconds

△: 30 seconds or more to less than 40 seconds

X: 40 seconds or more

<VD stain evaluation criteria>

◎ : Less than 5

○: 5 or more to less than 10

△: 10 or more to less than 15

X: 15 or more

Experimental Example 2: Evaluation of adhesion (pattern peeling)

The colored photosensitive resin composition according to the above Examples and Comparative Examples was coated on a 2-inch square glass substrate (EAGLE XG, manufactured by Corning) by spin coating, and then the glass substrate on which the coating film was formed was put into a decompression chamber so that the final pressure was 65 Pa. Drying under reduced pressure was carried out so as to become. Subsequently, a test photomask having a line/space pattern of 1 μm to 100 μm was placed on the thin film, and ultraviolet rays were irradiated at a distance of 300 μm from the test photomask. At this time, the ultraviolet light source was irradiated at 60 mJ/cm 2 using a 1KW high-pressure mercury lamp containing all of g, h, and i rays, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes and developed. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230° C. for 20 minutes to prepare a colored pattern. The thickness of the colored pattern prepared above was 2.4 μm.

The color pattern was photographed with an optical microscope to evaluate adhesion according to the criteria below, and the results are shown in FIGS. 2 to 5 and Table 2 below.

<Adhesion (Pattern Peeling) Evaluation Criteria>

◎: No peeled pattern (see Fig. 2)

○: Peeled pattern size is less than 20 μm (see FIG. 3)

△: Exfoliated pattern size less than 30 μm (see FIG. 4)

X: Exfoliated pattern size of 30 μm or more (see FIG. 5)

VD TIME VD stain adhesion Example 1 △ △ △ Example 2 O O △ Example 3 O O △ Example 4 △ △ O Example 5 O O O Example 6 O O O Example 7 ◎ ◎ ◎ Example 8 ◎ ◎ O Comparative Example 1 △ X △ Comparative Example 2 △ O X Comparative Example 3 △ X O Comparative Example 4 △ O X

Referring to Table 2, in the case of preparing a colored pattern using the colored photosensitive resin composition according to the embodiment, even if the pre-bake process is omitted, peeling of the pattern does not occur, and it can be confirmed that the adhesion is excellent. In the case of preparing a colored pattern using the colored photosensitive resin composition according to the example, it can be confirmed that peeling of the pattern occurs when the pre-bake process is omitted.

Claims (9)

In the colored photosensitive resin composition capable of pattern formation without a pre-bake process,
(A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator and (E) a solvent;
The (A) colorant includes an acidic dye having an acidic group of sulfonic acid or carboxylic acid,
The (E) solvent is colored, characterized in that it contains at least one of MMB (3-methoxy-3-methyl-1-butanol) and MMB-Ac (3-methoxy-3-methyl-1-butyl acetate) A photosensitive resin composition.
The method of claim 1,
The (E) solvent is a colored photosensitive resin composition, characterized in that it comprises MMB (3-methoxy-3-methyl-1-butanol) and MMB-Ac (3-methoxy-3-methyl-1-butyl acetate).
The method of claim 1,
The colored photosensitive resin composition comprising 1 to 20% by weight of at least one of MMB and MMB-Ac based on the total weight of the solvent (E).
The method of claim 1,
The (D) photopolymerization initiator is a colored photosensitive resin composition comprising at least one of an oxime-based photopolymerization initiator represented by the following formula (1) or an oxime-based photopolymerization initiator represented by the following formula (2):
[Formula 1]

In Formula 1,
R ₁ is

ego;
R ₂ and R ₃ are each independently an alkyl group having 1 to 8 carbon atoms unsubstituted or substituted with a hydroxyl group or an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group or a diphenylsulfide group;
R ₄ is an alkylene group having 1 to 4 carbon atoms;
R ₅ is a cycloalkyl group having 3 to 8 carbon atoms.
[Formula 2]

In Formula 2,
R ₆ and R ₇ are each independently a C1 to C20 linear or branched alkyl group, a C3 to C20 cycloalkyl group, a C4 to C20 cycloalkylalkyl group, a C4 to C20 alkylcycloalkyl group, a C3 to C20 heteroaryl group, or It is an aryl group of C6 to C20, and hydrogen contained in the alkyl group, cycloalkyl group, cycloalkylalkyl group, alkylcycloalkyl group, heteroaryl group or aryl group is each independently a halogen, a phenyl group, a nitro group, a hydroxyl group, a carboxyl group, a sulfonic acid substituted or unsubstituted with one or more groups selected from the group consisting of a group, an amino group, a cyano group, and an alkoxy group;
X and Y are each independently hydrogen, a C1 to C20 linear or branched alkyl group, a C3 to C20 cycloalkyl group, a C4 to C20 cycloalkylalkyl group, a C4 to C20 alkylcycloalkyl group or a C7 to C20 aralkyl group, wherein Hydrogen contained in an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an alkylcycloalkyl group, or an aralkyl group is each independently selected from the group consisting of a halogen, a nitro group, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group, a cyano group, and an alkoxy group. substituted or unsubstituted with one or more groups,
M is a group derived from carbazole, fluorene, dibenzofuran or dibenzothiophene unsubstituted or substituted with a C1 to C5 linear alkyl group.
The method of claim 4,
The oxime-based photopolymerization initiator represented by Formula 1 includes a compound represented by Formula 3 below, and the compound represented by Formula 2 includes a compound represented by Formula 4 below.
[Formula 3]

[Formula 4]

The method of claim 1,
With respect to the total weight of solids in the colored photosensitive resin composition,
The (A) colorant is included in 5 to 60% by weight,
The (B) alkali-soluble resin is contained in 10 to 80% by weight,
The (C) photopolymerizable compound is included in 5 to 50% by weight,
The (D) photopolymerization initiator is included in an amount of 0.5 to 6% by weight,
The (E) solvent is colored photosensitive resin composition, characterized in that contained in 60 to 90% by weight based on the total weight of the colored photosensitive resin composition.
Applying the colored photosensitive resin composition of any one of claims 1 to 6 on a substrate;
drying the substrate coated with the colored photosensitive resin under reduced pressure;
exposing the substrate dried under reduced pressure;
developing the exposed substrate; and
A method of forming a colored pattern, comprising: post-baking the developed substrate, and not including a pre-bake process.
A color filter comprising a colored pattern made of the colored photosensitive resin composition of any one of claims 1 to 6.
A display device comprising the color filter of claim 8.

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