KR102535173B1 - A red photosensitive resin composition, a color filter comprising the same, and a display devide comprising the color filter - Google Patents

Abstract

The present invention is a red photosensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator and (E) a solvent, wherein the (A) colorant is C.I. Pigment Red 179 and C.I. Pigment Red 264, and the (D) photopolymerization initiator includes at least one selected from the group consisting of carbazole-based and fluorene oxime-based, and prepared from the red photosensitive resin composition The thin film provides a red photosensitive resin composition having a spectral transmittance of 10% or less in the range of 590 nm to 595 nm, a color filter manufactured using the same, and a display device including the color filter.

Description

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

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

Color filters are widely used in various display devices such as imaging devices and liquid crystal displays (LCDs), and their application range is rapidly expanding. The color filter used in the imaging device, the liquid crystal display device, etc. consists of a coloring pattern of three colors of red, green, and blue, or yellow, magenta, and cyan ( Cyan) is composed of three color coloring patterns.

Each color pattern of the color filter is generally formed using a colored photosensitive resin composition containing a colorant such as a pigment or dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. Color pattern processing using the colored photosensitive resin composition is usually performed through a lithography process.

Color filters are essential materials for liquid crystal display materials, organic light emitting devices, displays, etc., and require excellent reliability characteristics such as solvent resistance and adhesion. In addition, color filters with improved color purity according to the recent trend of display screens and high-definition screens. technology development is required.

Korean Patent Registration No. 10-1648607 discloses an ink composition with improved contrast ratio reduction under an external light source, a color filter manufactured using the same, and a technology for a display device including the color filter, but the reliability deteriorates during low temperature curing. There is a problem, and it seems that it is not sufficient in terms of improving the color purity of the RED spectrum.

Republic of Korea Patent Registration No. 10-1648607

The present invention is to improve the above-mentioned conventional technical problems, and at the same time as improving the color purity of the RED spectrum, an object of the present invention is to provide a red photosensitive resin composition having excellent reliability such as solvent resistance and adhesion.

In addition, an object of the present invention is to improve color characteristics of a red device including a thin film manufactured using the red photosensitive resin composition.

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

In order to achieve the above object, the present invention is a red photosensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator and (E) a solvent, wherein the (A) The colorant is C.I. Pigment Red 179 and C.I. Pigment Red 264, and the (D) photopolymerization initiator includes at least one selected from the group consisting of carbazole-based and fluorene oxime-based, and prepared from the red photosensitive resin composition The thin film to provide a red photosensitive resin composition having a spectral transmittance in the range of 590 nm to 595 nm of 10% or less.

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

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

The red photosensitive resin composition of the present invention contains C.I. Pigment Red 179 and C.I. By including at least one member selected from the group consisting of Pigment Red 264 and at least one member selected from the group consisting of carbazole and fluorene oxime as a photopolymerization initiator, 590 nm to 595 nm for a thin film manufactured using the same It can satisfy the characteristics that the maximum spectral transmittance of the range is 10% or less and the spectral transmittance of 600nm or more is 20% or more, thereby improving the color purity of the RED spectrum, and at the same time achieving excellent effects in solvent resistance and adhesion. .

In addition, an effect of improving color characteristics of a red device including a thin film manufactured using the red photosensitive resin composition is provided.

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

1 is a diagram showing criteria for evaluating adhesion in the present invention.
Figure 2 is a graph measuring the spectral transmittance of thin films made of red photosensitive resin compositions of Examples and Comparative Examples according to the present invention.
FIG. 3 is an enlarged graph of a portion having a wavelength range of 590 nm to 600 nm in FIG. 2 .

The present invention is a red photosensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator and (E) a solvent, wherein the (A) colorant is C.I. Pigment Red 179 and C.I. Pigment Red 264, and the (D) photopolymerization initiator includes at least one selected from the group consisting of carbazole-based and fluorene oxime-based, and prepared from the red photosensitive resin composition The thin film provides a red photosensitive resin composition having a spectral transmittance of 10% or less in the range of 590 nm to 595 nm, a color filter manufactured using the same, and a display device including the color filter.

The red photosensitive resin composition according to the present invention contains C.I. Pigment Red 179 and C.I. By including at least one member selected from the group consisting of Pigment Red 264 and at least one member selected from the group consisting of a carbazole-based and a fluorene oxime-based photopolymerization initiator, the color filter manufactured using the same has a 590 nm to 595 nm The color purity of the RED spectrum can be improved by satisfying the characteristics that the maximum spectral transmittance in the range is 10% or less and the spectral transmittance of 600nm or more is 20% or more, and at the same time, reliability such as solvent resistance and adhesion can also provide very excellent effects. can

Therefore, it is possible to provide an effect of improving color characteristics of a red device including a thin film manufactured using the red photosensitive resin composition according to the present invention.

Red photosensitive resin composition

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

(A) colorant

The colorant is C.I. Pigment Red 179 and C.I. It is characterized in that it includes at least one selected from the group consisting of Pigment Red 264, and may further include at least one pigment (a1), at least one dye (a3), or a mixture thereof.

As the colorant, C.I. Pigment Red 179 and C.I. As it contains at least one selected from the group consisting of Pigment Red 264, as can be seen in FIG. 2, the spectral transmittance of the color filter prepared using this is shifted to the right as a whole, thereby improving the color purity of the RED spectrum. can improve

That is, as the spectral transmittance of the color filter moves to the right side of the red wavelength series, the maximum spectral transmittance in the range of 590 nm to 595 nm may be 10% or less, and the spectral transmittance in the range of 600 nm or more may be 20% or more. The maximum spectral transmittance may be 1% or more to 10% or less, and the spectral transmittance of 600 nm or more may be 20% or more to 100% or less.

(a1) pigment

As the pigment, organic pigments or inorganic pigments generally used in the art may be used, and these may be used alone or in combination of two or more. In addition, if necessary, the pigment is resin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment of the pigment surface using a polymer compound, etc., atomization treatment by a sulfuric acid atomization method, etc., to remove impurities A washing treatment with an organic solvent or water 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, 180, 192, 208, 215, 216, 224, 242, 254 and 255;

C.I Pigment Black 1 and 7;

The pigment is preferably C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255.

The pigment may be included in an amount of 5 to 60% by weight, preferably 10 to 45% by weight, based on the total weight of the solid content in the red photosensitive resin composition. When the pigment is included within the above range, the color density of the pixel is sufficient even when a thin film is formed, and the omission of non-pixel parts is not deteriorated during development, so residue is not generated.

As the pigment, it is preferable to use a pigment dispersion in which the particle size of the pigment is uniformly dispersed. As an example of a method for uniformly dispersing the particle size of the pigment, a method of dispersing treatment by containing a pigment dispersant (a2) may be mentioned. According to the above method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained. there is.

(a2) pigment dispersant

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 red photosensitive resin composition, and it is preferable that the gelation process is easy after atomization and dispersion of the pigment.

(a3) dye

The dye may be used without limitation as long as it has solubility in organic solvents. Preferably, it is preferable to use a dye capable of securing reliability such as solubility in an alkaline 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. 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 ; 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 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, 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. 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;

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;

These dyes may be used alone or in combination of two or more.

When the dye is included in the colorant, the content of the dye may be included as 0.5 to 80% by weight, preferably 0.5 to 60% by weight, and more preferably 1 to 50% by weight based on 100% by weight of the solid content of the colorant. When the dye is included within the above content range, it is possible to prevent a problem of deterioration in reliability in which the dye is eluted by an organic solvent after pattern formation, and sensitivity is increased, which is preferable.

The content of the colorant may be included in the range of 5 to 60% by weight, preferably 10 to 45% by weight, based on the total weight of solids in the red 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 solids in the red photosensitive resin composition means the total weight of the components other than the solvent of the red photosensitive resin composition.

(B) alkali soluble resin

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

The alkali-soluble resin may be included in an amount of 10 to 80% by weight, preferably 10 to 70% by weight, based on the total weight of solids in the red 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.

The acid value of the alkali-soluble resin is preferably 30 mg·KOH/g to 150 mg·KOH/g, and thus compatibility with the dye and stability over time of the red photosensitive resin composition may be improved. When the acid value of the alkali-soluble resin is less than 30 mg·KOH/g, it is difficult to secure a sufficient development rate for the red photosensitive resin composition, and when it exceeds 150 mg·KOH/g, adhesion to the substrate is reduced, resulting in short circuit of the pattern. This is likely to occur, and a compatibility problem with the dye may cause the dye to precipitate in the red photosensitive resin composition, or the stability over time of the red 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.

The sum of the hydroxyl values of the alkali-soluble resin and the photopolymerizable compound described below is preferably 50 mg·KOH/g to 250 mg·KOH/g. If the sum of the alkali-soluble resin and the hydroxyl group of the photopolymerizable compound is less than 50 mg KOH / g, a sufficient development rate cannot be secured, and if it exceeds 250 mg KOH / g, the dimensional stability of the pattern formed The linearity of the pattern is easily deteriorated, and the compatibility with the dye is deteriorated, 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 may be prepared by copolymerizing the ethylenically unsaturated monomer having a carboxyl group and the ethylenically unsaturated monomer (b2) having a hydroxyl group. Alternatively, the alkali-soluble resin may be prepared by copolymerizing the copolymer of the ethylenically unsaturated monomer having a carboxyl group with the compound (b3) having a 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 copolymerization of the unsaturated monomer (b4).

(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 a photopolymerization initiator 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, N-vinylpy Rolidone etc. are mentioned. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. , bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like. Specific examples of other polyfunctional monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Pentaerythritol hexa(meth)acrylate etc. are mentioned. Among these, bifunctional or higher functional monomers are preferably used.

The photopolymerizable compound may be included in an amount of 5 to 50% by weight, preferably 7 to 45% by weight, based on the total weight of the solid content in the red photosensitive resin composition. When the photopolymerizable compound is contained within the above range, it is preferable because the strength and smoothness of the pixel portion tend to be good.

(D) photopolymerization initiator

The photopolymerization initiator is characterized in that it includes at least one selected from the group consisting of carbazole-based and fluorene oxime-based. Accordingly, reliability such as solvent resistance and adhesion of the red photosensitive resin composition according to the present invention including a specific colorant can be improved.

The photopolymerization initiator preferably includes a compound represented by Formula 1 below.

[Formula 1]

(In Formula 1, A is CH or a nitrogen atom,

R ₁ to R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a group represented by the following formula (2), COR ₁₆ or NO ₂ ,

R ₁₃ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, or It is a naphthyl group,

R ₁₆ is an aryl group having 6 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms.)

[Formula 2]

(In Formula 2, R ₁₄ is a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a naphthyl group,

R ₁₅ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms;

wherein X is CO or a direct connection;

* is a bond with a carbon atom or nitrogen atom.)

In the compound represented by Formula 1, A is -CH- or a nitrogen atom, and R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or at least one pair of R ₇ and R ₈ may be a group represented by Formula 3 below.

[Formula 3]

(In Formula 3, R ₉ to R ₁₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted phenyl group.)

The photopolymerization initiator may include, in addition to the compound represented by Formula 1, a photopolymerization initiator commonly used in this field in an amount of 5 to 40% by weight based on the total weight of the photopolymerization initiator.

Examples of the commonly used photopolymerization initiator include triazine-based compounds, acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, and oxime-based compounds.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethine Toxystyryl)-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-tolyl-4,6-bis(trichloromethyl)-s-triazine, 2- Pipenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloro butyl)-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.

Specific examples of the acetophenone-based compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and p-t-butyltrichloroacetophenone. , p-t-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane -1-one etc. are mentioned.

Examples of the benzophenone-based compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'- bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

The thioxanthone-based compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone. Oxanthone, 2-chloro thioxanthone, etc. are mentioned.

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

Examples of the oxime-based compound include 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione and 1-(o-acetyloxime)-1-[9-ethyl- 6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone etc. are mentioned.

In addition to those exemplified above, carbazole-based compounds, diketone compounds, sulfonium borate-based compounds, diazo-based compounds, and biimidazole-based compounds may also be used as photopolymerization initiators.

The photopolymerization initiator may be included in an amount of 0.1 to 10% by weight, more preferably 3 to 8% by weight, based on the total weight of the solid content in the red photosensitive resin composition. When the photopolymerization initiator is included within the above range, photopolymerization may sufficiently occur during exposure in the pattern forming process, and transmittance may not decrease due to remaining unreacted initiator after photopolymerization.

(E) Solvent

As long as the solvent is effective in dissolving other components included in the red photosensitive resin composition, solvents used in conventional red photosensitive resin compositions may be used without particular limitation, and in particular, ethers, aromatic hydrocarbons, ketones, alcohols, and esters. or amides are preferred.

The solvent is specifically 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, propylene glycol monomethyl ether acetate, Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, methyl ethyl ketone , ketones such as acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin, ethyl 3-ethoxypropionate, 3- Cyclic esters, such as esters, such as methoxy methyl propionate, and (gamma)-butyrolactone, etc. are mentioned.

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

Each of the above-exemplified solvents may be used alone or in combination of two or more, and 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 red 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 red photosensitive resin composition according to the present invention may further include additives as needed, and as specific examples, at least one selected from a dispersing agent, a wetting agent, a silane coupling agent, and an aggregation inhibitor may be used.

Commercially available surfactants may be used as the dispersant, and examples of the surfactant include silicone-based surfactants, fluorine-based surfactants, silicone-based surfactants having fluorine atoms, and mixtures thereof. Examples of the silicone-based surfactant include a surfactant having a siloxane bond. Commercially available products include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone 29SHPA, Toray Silicone SH30PA, polyether modified silicone oil SH8400 (manufactured by Toray Silicone Co., Ltd.), KP321 . can be heard

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Prolinate (trade name) FC430, Prolinate FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapack (trade name) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, Megapack F183, Megapack R30 (manufactured by Dainippon Ink Kagaku Kogyo Co., Ltd.), F-top (brand name) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Shin-Akitaka Sei Co., Ltd.), Seo Suffron (trade name) S381, Suffron S382, Suffron SC101, Suffron SC105 (manufactured by Asahigaras Co., Ltd.), E5844 (manufactured by Daikin Fine Chemicals Co., Ltd.), BM-1000, BM-1100 (products) Name: Manufactured by BMChemie) and the like.

Examples of the silicon-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specifically, Megapack (trade name) R08, Megapack BL20, Megapack F475, Megapack F477, Megapack F443 (manufactured by Dainippon Ink Kagaku Kogyo Co., Ltd.) and the like are exemplified.

Examples of the humectant include glycerin, diethylene glycol, ethylene glycol, and the like, and may include one or more selected from among them.

Examples of the silane coupling agent include aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Commercially available products include SH6062 and SZ6030 (Toray-Dow Corning Silicon co., Ltd.), KBE903, KBM803 (manufactured by Shin-Etsu silicone co., Ltd.).

Examples of the aggregation inhibitor include sodium polyacrylate.

Color filters and display devices

In addition, the present invention provides a color filter including a color pattern made of the red photosensitive resin composition according to the present invention, and a display device including the color filter.

A display device capable of including such a color filter may include a liquid crystal display, 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.

The color filter may be prepared by coating the above-described red photosensitive resin composition of the present invention on a substrate, photocuring, and developing to form a pattern.

First, a red photosensitive resin composition is applied to a substrate and then heated and dried to remove volatile components such as a solvent to obtain a smooth coating film.

As the coating method, for example, spin coating, casting coating, roll coating, slit and spin coating, or slit coating may be used. After application, heat drying (prebaking) or drying under reduced pressure is followed by heating to volatilize volatile components such as solvents. Here, the heating temperature is usually 70 to 200°C, preferably 80 to 130°C. The coating film thickness after heat drying is usually about 1 to 8 μm. 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.

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. Incidentally, in the following examples and comparative examples, "%" and "parts" indicating content are based on mass unless otherwise specified.

Examples and Comparative Examples: Preparation of red photosensitive resin composition

Example 1

(A) C.I. 25 parts of Pigment Red 179 (pigment), 4 parts of BYK-2001 (BYK) as a pigment dispersant, and 71 parts of propylene glycol monomethyl ether acetate were mixed, and 30 parts of a pigment dispersion solution in which the pigment was sufficiently dispersed using a bead mill, ( B) 10 parts of SPCY-6L (Showa Polymer Co.) as an alkali-soluble resin, (C) 5 parts of A9550 (Shin Nakamura Co.) as a photopolymerizable compound, (D) 1 part of OXE-02 (BASF Co.) as a photopolymerization initiator, and (E) A red photosensitive resin composition according to Example 1 was prepared by mixing 54 parts of propylene glycol monomethyl ether acetate as a solvent.

Example 2

(A) C.I. 25 parts of Pigment Red 264 (pigment), 4 parts of BYK-2001 (BYK) as a pigment dispersant and 71 parts of propylene glycol monomethyl ether acetate were mixed, and 30 parts of a pigment dispersion solution in which the pigment was sufficiently dispersed using a bead mill, ( B) 10 parts of SPCY-6L (Showa Polymer Co.) as an alkali-soluble resin, (C) 5 parts of A9550 (Shin Nakamura Co.) as a photopolymerizable compound, (D) 1 part of OXE-02 (BASF Co.) as a photopolymerization initiator, and (E) A red photosensitive resin composition according to Example 2 was prepared by mixing 54 parts of propylene glycol monomethyl ether acetate as a solvent.

Example 3

(A) C.I. Pigment Red 179 (pigment) 12.5 parts, C.I. 12.5 parts of Pigment Red 264 (pigment), 4 parts of BYK-2001 (BYK) as a pigment dispersant, and 71 parts of propylene glycol monomethyl ether acetate were mixed, and 30 parts of a pigment dispersion solution in which the pigment was sufficiently dispersed using a bead mill, ( B) 10 parts of SPCY-6L (Showa Polymer Co.) as an alkali-soluble resin, (C) 5 parts of A9550 (Shin Nakamura Co.) as a photopolymerizable compound, (D) 1 part of OXE-02 (BASF Co.) as a photopolymerization initiator, and (E) A red photosensitive resin composition according to Example 3 was prepared by mixing 54 parts of propylene glycol monomethyl ether acetate as a solvent.

Example 4

(A) C.I. 25 parts of Pigment Red 179 (pigment), 4 parts of BYK-2001 (BYK) as a pigment dispersant, and 71 parts of propylene glycol monomethyl ether acetate were mixed, and 30 parts of a pigment dispersion solution in which the pigment was sufficiently dispersed using a bead mill, ( B) 10 parts of SPCY-6L (Showa Polymer Co.) as an alkali-soluble resin, (C) 5 parts of A9550 (Shin Nakamura Co.) as a photopolymerizable compound, (D) 1 part of OXE-03 (BASF Co.) as a photopolymerization initiator, and (E) A red photosensitive resin composition according to Example 4 was prepared by mixing 54 parts of propylene glycol monomethyl ether acetate as a solvent.

Example 5

(A) C.I. 25 parts of Pigment Red 179 (pigment), 4 parts of BYK-2001 (BYK) as a pigment dispersant, and 71 parts of propylene glycol monomethyl ether acetate were mixed, and 30 parts of a pigment dispersion solution in which the pigment was sufficiently dispersed using a bead mill, ( B) 10 parts of SPCY-6L (Showa Polymer Co.) as an alkali-soluble resin, (C) 5 parts of A9550 (Shin Nakamura Co.) as a photopolymerizable compound, (D) 1 part of SPI-03 (Samyang Co.) as a photopolymerization initiator and (E) A red photosensitive resin composition according to Example 5 was prepared by mixing 54 parts of propylene glycol monomethyl ether acetate as a solvent.

Comparative Example 1

(A) C.I. 25 parts of Pigment Red 254 (pigment), 4 parts of BYK-2001 (BYK) as a pigment dispersant, and 71 parts of propylene glycol monomethyl ether acetate were mixed, and 30 parts of a pigment dispersion solution in which the pigment was sufficiently dispersed using a bead mill, ( B) 10 parts of SPCY-6L (Showa Polymer Co.) as an alkali-soluble resin, (C) 5 parts of A9550 (Shin Nakamura Co.) as a photopolymerizable compound, (D) 1 part of OXE-02 (BASF Co.) as a photopolymerization initiator, and (E) A red photosensitive resin composition according to Comparative Example 1 was prepared by mixing 54 parts of propylene glycol monomethyl ether acetate as a solvent.

Comparative Example 2

(A) C.I. 25 parts of Pigment Red 177 (pigment), 4 parts of BYK-2001 (BYK) as a pigment dispersant, and 71 parts of propylene glycol monomethyl ether acetate were mixed, and 30 parts of a pigment dispersion solution in which the pigment was sufficiently dispersed using a bead mill, ( B) 10 parts of SPCY-6L (Showa Polymer Co.) as an alkali-soluble resin, (C) 5 parts of A9550 (Shin Nakamura Co.) as a photopolymerizable compound, (D) 1 part of OXE-02 (BASF Co.) as a photopolymerization initiator, and (E) A red photosensitive resin composition according to Comparative Example 2 was prepared by mixing 54 parts of propylene glycol monomethyl ether acetate as a solvent.

Comparative Example 3

(A) C.I. 25 parts of Pigment Red 179 (pigment), 4 parts of BYK-2001 (BYK) as a pigment dispersant, and 71 parts of propylene glycol monomethyl ether acetate were mixed, and 30 parts of a pigment dispersion solution in which the pigment was sufficiently dispersed using a bead mill, ( B) 10 parts of SPCY-6L (Showa Polymer Co.) as an alkali-soluble resin, (C) 5 parts of A9550 (Shin Nakamura Co.) as a photopolymerizable compound, (D) 1 part of I-369 (Ciba Co.) as a photopolymerization initiator and (E) A red photosensitive resin composition according to Comparative Example 3 was prepared by mixing 54 parts of propylene glycol monomethyl ether acetate as a solvent.

Comparative Example 4

(A) C.I. 25 parts of Pigment Red 179 (pigment), 4 parts of BYK-2001 (BYK) as a pigment dispersant, and 71 parts of propylene glycol monomethyl ether acetate were mixed, and 30 parts of a pigment dispersion solution in which the pigment was sufficiently dispersed using a bead mill, ( B) 10 parts of SPCY-6L (Showa Polymer Co.) as an alkali-soluble resin, (C) 5 parts of A9550 (Shin Nakamura Co.) as a photopolymerizable compound, (D) 1 part of I-907 (Ciba Co.) as a photopolymerization initiator and (E) A red photosensitive resin composition according to Comparative Example 4 was prepared by mixing 54 parts of propylene glycol monomethyl ether acetate as a solvent.

Preparation Example: Preparation of a color filter using a red photosensitive resin composition

The red photosensitive resin composition according to Examples 1 to 5 and Comparative Examples 1 to 4 was coated on a bare glass substrate by spin coating, then placed on a heating plate and maintained at 100 ° C. for 2 minutes to form a thin film. Subsequently, a test photomask having a pattern for changing the transmittance stepwise in the range of 1 to 100% and a line/space pattern of 1 μm to 100 μm was placed on the thin film, and an interval between the test photomask and the test photomask was set at 200 μm, and ultraviolet rays was investigated. At this time, the ultraviolet light source was irradiated with an illuminance of 50 mJ/cm 2 using a 1 KW high-pressure mercury lamp containing all of the g, h, and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet light was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes and developed. The post-process Bake was performed on a 230°C hotplate for 20 minutes. The film thickness of the color filter of the red photosensitive resin composition according to Examples 1 to 5 and Comparative Examples 1 to 4 prepared according to this method was 2.5 μm.

Test Example: Evaluation of physical properties of a color filter using a red photosensitive resin composition

1. Solvent resistance evaluation

The color filter prepared according to the above Preparation Example was immersed in a NMP solvent at 23° C. for 30 minutes, and the color change before and after immersion was compared and evaluated. At this time, the color change is calculated by the following [Equation 1], and the values calculated by the following [Equation 1] are shown in Table 1 below.

[Equation 1]

ΔEab* =[(ΔL*) ² +(Δa*) ² +(Δb*) ² ] ^1/2

The [Equation 1] represents the color change in the three-dimensional colorimetric system defined by L*, a*, and b*, and the smaller the color change value calculated by [Equation 1], the higher the reliability of the solvent resistance. It is possible to manufacture color filters.

<Evaluation Criteria>

○: Excellent solvent resistance (no change in pattern, △(Eab*) less than 3.0)

△: Good solvent resistance (there is little change in pattern, △(Eab*) is 3.0 or more and less than 5.0)

×: Poor solvent resistance (pattern changes or △(Eab*) is 5.0 or more)

2. Adhesion evaluation

The color filter prepared according to the Preparation Example was immersed in a NMP solvent at room temperature, waited for 10 minutes, and then OK or NG was determined through whether or not the formed pattern was detached. 1 is a diagram showing criteria for evaluating such adhesion. If the pattern remains after immersion, it is determined as OK, and if the pattern is separated after immersion, it is determined as NG, and the results are shown in Table 1 below.

3. Spectral Transmittance Measurement

The spectral transmittance of the color filter prepared according to the preparation example was measured using a microscopic spectrophotometer, OSP-SP2000 (Olympus Co.). The results are shown in FIGS. 2 and 3, and the spectral transmittance in the range of 590 nm to 595 nm is shown in Table 1 below.

On the other hand, since Examples 4 to 5 and Comparative Examples 3 to 4 show substantially the same spectral transmittance as Example 1 including the same colorant, FIGS. 2 and 3 show Examples 1 to 3 and Comparative Examples 1 to 2 Only the spectral transmittance is shown.

division solvent resistance adhesion 590~595nm
transmittance Example 1 O OK 3-10% Example 2 O OK 4-10% Example 3 O OK 2-9% Example 4 O OK 3-10% Example 5 O OK 3-10% Comparative Example 1 O OK 70-81% Comparative Example 2 O OK 12-29% Comparative Example 3 X NG 3-10% Comparative Example 4 X NG 3-10%

Referring to Table 1, FIGS. 2 and 3, Examples 1 to 5 according to the present invention have a spectral transmittance of 10% or less in the range of 590 nm to 595 nm and a spectral transmittance of 20% or more in the range of 600 nm or more, Comparative Example 1 and 2, it can be confirmed that the spectral transmittance is shifted to the right as a whole. That is, in the case of a color filter manufactured using the red photosensitive resin composition according to the present invention, since the spectral transmittance is concentrated in the red-based region, it can exhibit better RED spectral color purity.

In addition, while Examples 1 to 5 using a carbazole-based or fluorene oxime-based compound as an initiator showed excellent effects in both solvent resistance and adhesiveness, Comparative Example 3 using an initiator other than the carbazole-based and fluorene oxime-based compound And in the case of 4, it can be confirmed that both solvent resistance and adhesion are poor.

Therefore, in the case of manufacturing a color filter using the red photosensitive resin composition according to the present invention, the highest spectral transmittance in the range of 590 nm to 595 nm is 10% or less, and the spectral transmittance of 600 nm or more is 20% or more. While the color purity of the RED spectrum is improved, a color filter having excellent solvent resistance and adhesion can be obtained.

Claims (7)

A red photosensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent,
The (A) coloring agent includes at least one selected from the group consisting of CI Pigment Red 179 and CI Pigment Red 264,
The (D) photopolymerization initiator includes a fluorene oxime-based compound,
A thin film made of the red photosensitive resin composition has a spectral transmittance of 10% or less in the range of 590 nm to 595 nm.
The method of claim 1,
The red photosensitive resin composition, characterized in that the thin film made of the red photosensitive resin composition has a spectral transmittance of 600 nm or more of 20% or more.
The method of claim 1,
The (D) photopolymerization initiator is a red photosensitive resin composition, characterized in that it comprises a compound represented by the following formula (1).
[Formula 1]

(In Formula 1, A is CH,
R ₁ to R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a group represented by the following formula (2), COR ₁₆ or NO ₂ ,
R ₁₃ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, or It is a naphthyl group,
R ₁₆ is an aryl group having 6 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms.)
[Formula 2]

(In Formula 2, R ₁₄ is a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a naphthyl group,
R ₁₅ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms;
wherein X is CO or a direct connection;
* is a bond with a carbon atom or nitrogen atom.)
The method of claim 3,
In Formula 1, at least one pair of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ and R ₈ is represented by the following Formula 3 A red photosensitive resin composition characterized by being a group represented by:
[Formula 3]

(In Formula 3, R ₉ to R ₁₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted phenyl group.)
The method of claim 1,
With respect to the total weight of solids in the red photosensitive resin composition,
5 to 60% by weight of the (A) colorant;
10 to 80% by weight of the (B) alkali-soluble resin;
5 to 50% by weight of the (C) photopolymerizable compound, and
0.1 to 10% by weight of the (D) photopolymerization initiator;
The (E) solvent is a red photosensitive resin composition, characterized in that contained in 60 to 90% by weight based on the total weight of the red photosensitive resin composition.
A color filter comprising a colored pattern made of the red photosensitive resin composition of any one of claims 1 to 5.
A display device comprising the color filter of claim 6.

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