JP6625511B2 - Colored photosensitive resin composition, color filter and display device including the same - Google Patents

Description

The present invention relates to a colored photosensitive resin composition, a color filter and a display device containing the same, and more particularly, a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and TECHNICAL FIELD The present invention relates to a colored photosensitive resin composition excellent in color, a color filter containing the same and a display device.

Electronic display devices used for office automation equipment, portable small televisions, video camera viewfinders, and the like include liquid crystal display devices (LCDs), plasma display panels (PDPs), and organic light emitting diodes (PDPs). organic light emitting diode (OLED), etc., and technical research related thereto is actively being conducted.

The liquid crystal display device has advantages such as light weight, thinness, low cost, low power consumption driving, and excellent integration with an integrated circuit, and has a use range for notebook computers, monitors, and television images. It has spread. Such a liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and an ITO pixel electrode are formed, an active circuit portion including a liquid crystal layer, a thin film transistor, and a storage capacitor layer, and an upper portion on which an ITO pixel electrode is formed. And a substrate.

The color filter is manufactured by coating a fine region colored with three or more colors on a solid-state imaging device or a transparent substrate. Such a colored thin film is usually formed by a dyeing method, an electrodeposition method, a pigment dispersion method, or the like. Recently, a pigment dispersion method having excellent heat resistance and durability has been used.

In the pigment dispersion method, a series of processes of coating, exposing, developing, and thermally curing a photopolymerizable composition containing a colorant on a transparent substrate provided with a light-shielding layer (black matrix) is performed by coloring. This is the method by which the thin film is formed. The pigment dispersion method has the advantages that the most important properties of a color filter, heat resistance and durability, can be improved, and the film thickness can be maintained uniform.

The colored photosensitive resin composition used in the production of a color filter by a pigment dispersion method generally includes a binder resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent and other additives. Become.

2. Description of the Related Art In recent years, a color filter manufacturing process has been manufactured as a continuous process capable of mass production. Recently, a color filter has been manufactured using a colored photosensitive resin composition having a small pigment particle diameter according to high quality specifications. This results in a decrease in process yield as stains on the fine pattern of the color filter increase.

Patent Literature 1 provides a colored photosensitive resin composition that can improve the above-described problem, but has a problem of low developability.

Korean Patent Publication No. 10-2009-0072754

An object of the present invention is to provide a colored photosensitive resin composition which does not cause development stains and has excellent developability.

Another object of the present invention is to provide a color filter and a display device manufactured using the colored photosensitive resin composition.

To achieve the above objectives,
The present invention is a colored photosensitive resin composition containing a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The alkali-soluble resin includes monomers represented by the following chemical formulas 1 and 2,
The molecular weight of the alkali-soluble resin is 12000 to 17000, the acid value is 60 to 120 KOHmg / g,
The photopolymerization initiator provides a colored photosensitive resin composition containing an oxime ester fluorene derivative compound.

R _{1 to} R ₁₀ are the same or different and are each hydrogen or an alkyl group having 1 to 5 carbon atoms.

The present invention also provides a color filter manufactured using the colored photosensitive resin composition.

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

The colored photosensitive resin composition of the present invention has the advantages that development stains are not generated, the developability is excellent, and the processability is easily ensured.

Further, the color filter and the display device manufactured using the colored photosensitive resin composition of the present invention have an effect of excellent color reproduction.

It is a photograph which shows that a development stain does not occur. It is a photograph which shows that development stain is good. It is a photograph which shows that a development stain is bad. It is a photograph which shows that it is excellent in developability. It is a photograph which shows that developability is bad.

Hereinafter, the present invention will be described in more detail.

The present invention is a colored photosensitive resin composition containing a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The alkali-soluble resin includes monomers represented by the following chemical formulas 1 and 2,
The molecular weight of the alkali-soluble resin is 12000 to 17000, the acid value is 60 to 120 KOHmg / g,
The photopolymerization initiator relates to a colored photosensitive resin composition containing an oxime ester fluorene derivative compound.

R _{1 to} R ₁₀ are the same or different and are each hydrogen or an alkyl group having 1 to 5 carbon atoms.

In the present invention, the use of an alkali-soluble resin containing the monomers of Formulas 1 and 2 and the use of an oxime ester fluorene derivative compound as a photopolymerization initiator does not cause development stains and has excellent developability. An attempt was made to provide a colored photosensitive resin composition.

Hereinafter, the colored photosensitive resin composition of the present invention will be described in detail for each component.

(A) Colorant In the present invention, the colorant includes one or more pigments, one or more dyes, or a mixture thereof, and preferably includes one or more pigments.

(A1) Pigment As the pigment, an organic pigment or an inorganic pigment generally used in the art can be used. Further, the pigment is, if necessary, a resin treatment, a surface treatment using a pigment derivative or the like into which an acidic group or a basic group is introduced, a graft treatment of the pigment surface with a polymer compound, a sulfuric acid atomization method, or the like. An atomizing treatment, a washing treatment with an organic solvent or water for removing impurities, a treatment for removing ionic impurities by an ion exchange method, or the like may be performed.

As the organic pigment, various pigments used for printing inks, inkjet inks and the like can be used.Specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, Examples include indoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthantrone pigments, indanthrone pigments, flavantron pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like.

Further, as the inorganic pigment, metal compounds such as metal oxides and metal complex salts can be used, and specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, Metal oxides or composite metal oxides such as antimony, carbon black, organic black pigments, titanium black, and pigments exhibiting black by mixing red, green, and blue are given.

In particular, examples of the organic pigment and the inorganic pigment include compounds classified as pigments in a color index (published by The society of Dyers and Colorists). More specifically, the following color indices ( CI), but are 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, 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.), 21, 28, 60, 64, and 76;
C. I. Pigment Green 7, 10, 15, 25, 36, 47, and 58;
C. I. Pigment Brown 28; and C.I. I. And pigments such as CI Pigment Black 1 and 7.

The pigments can be used alone or in combination of two or more.

C. I. Among the pigments, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 185, C.I. I. Pigment Orange 38, C.I. I. Pigment Red 122, C.I. I. Pigment Red 166, C.I. I. Pigment Red 177, C.I. I. Pigment Red 208, C.I. I. Pigment Red 242, C.I. I. Pigment red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Violet 23, C.I. I. Pigment Blue 15: 3, Pigment Blue 15: 6, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, and C.I. I. Pigment Green 58 is preferable.

The content of the pigment is 10 to 50% by weight, preferably 15 to 45% by weight, based on the total weight of the colored photosensitive resin composition. When the content of the pigment is in the range of 10 to 50% by weight, the effect of low viscosity, excellent storage stability, high dispersion efficiency, and increase in contrast ratio can be exhibited.

As the pigment, it is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of the method for uniformly dispersing the particle size of the pigment include a method in which a pigment dispersant (a2) is added and dispersion treatment is performed, and the method in which the pigment is uniformly dispersed in the solution by the method described above. A pigment dispersion can be obtained.

(A2) Pigment dispersant The pigment dispersant is added for deagglomeration and stability maintenance of the pigment. Specific examples of the pigment dispersant include cationic, anionic, nonionic and amphoteric. Surfactants such as polyester-based, polyester-based, and polyamine-based surfactants. These can be used alone or in combination of two or more.

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

Specific examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; and sodium dodecylbenzene sulfonate. And alkylaryl sulfonates such as sodium dodecylnaphthalenesulfonate.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymer, sorbitan Examples include fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Other examples include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethylene imines.

Further, the pigment dispersant preferably includes an acrylate-based dispersant containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA) (hereinafter, acrylate-based dispersant). Commercial products of the acrylate dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, and the like. The acrylate dispersants may be used alone or in combination of two or more. They can be mixed and used.

As the pigment dispersant, other resin-type pigment dispersants may be used in addition to the acrylate dispersant. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, in particular, polyurethanes, polycarboxylic acid esters represented by polyacrylates, unsaturated polyamides, polycarboxylic acids, and polycarboxylic acids. A) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl-containing polycarboxylic acids and their modified products, or free ( free) oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a carboxyl group with poly (lower alkyleneimine); (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- ( (Meth) acrylate ester copolymer, styrene-ma Ynoic acid copolymers, polyvinyl alcohol or water-soluble resin or a water-soluble polymeric compounds such as polyvinyl pyrrolidone; polyesters; modified polyacrylate; addition products of ethylene oxide / propylene oxide; and the like and phosphate esters.

Commercially available pigment dispersants of the other resin type include cationic resin dispersants such as, for example, BYK (Bik) Chemie's trade names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162. DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF product 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; brand names of Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; brand names of Kawaken Fine Chemicals: Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; trade name of Ajinomoto Co .: AJISPUR PB-821, Ajispar PB-822, Ajispar PB-823; trade name of Kyoeisha Chemical Co., Ltd .: Floren DOPA-17HF, Floren DOPA-15BHF, Floren DOPA -33 and Floren DOPA-44.

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

The content of the pigment dispersant is preferably 5 to 60% by weight, specifically 15 to 50% by weight based on the total weight of the colored photosensitive resin composition. When the above ranges are satisfied, there is an advantage that the phenomenon that the viscosity is increased is prevented, the pigment is easily atomized, and problems such as gelation after dispersion can be prevented.

(A3) Dye The dye can be used without limitation as long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye having solubility in an organic solvent and securing reliability such as solubility in an alkaline developer, heat resistance, and solvent resistance.

As the dye, it is possible to use an acid dye having an acidic group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, and a derivative thereof. And azo, xanthene and phthalocyanine acid dyes and their derivatives. Preferably, the dye is a compound classified as a dye in the Color Index (published by The Society of Dyers and Colorists), or a known dye described in Dyeing Note (Shirosen).

Specific examples of the dye include C.I. I. As a solvent dye,
C. I. Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, and 179;
C. I. Solvent Blue 5, 35, 36, 37, 44, 59, 67, and 70;
C. I. Solvent violet 8, 9, 13, 14, 36, 37, 47, and 49;
C. I. Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, and 163;
C. I. Solvent Orange 2, 7, 11, 15, 26, 41, 45, 56, and 62;
C. I. And dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35.

C. I. Among the solvent dyes, C.I. I. Solvent Yellow 14, 16, 21, 56, 151, 79, and 93; I. Solvent Red 8, 49, 89, 111, 122, 132, 146, and 179; I. Solvent Orange 41, 45, and 62; I. Solvent Blue 35, 36, 44, 45, and 70; and C.I. I. Solvent Violet 13 is preferred, and C.I. I. Solvent Yellow 21 and 79; I. Solvent Red 8, 122, and 132; and C.I. I. Solvent Oranges 45 and 62 are more preferred.

C.I. I. As an acid dye,
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, and 426;
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, and 251;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, and 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, 335, and 340;
C. I. Acid Violet 6B, 7, 9, 17, 19, and 66;
C. I. Dyes such as Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109;

C. I. Among the acid dyes, C.I. I. Acid yellow 42; I. Acid Red 92; I. Acid Blue 80, 90; C.I. I. Acid Green 27, and C.I. I. Acid violet 66 is preferred.

Further, C.I. I. As a direct dye,
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, and 250;
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, and 141;
C. I. Direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, and 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, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, and 293
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, and 104;
C. I. And dyes such as Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, and 82.

C.I. I. As a modant dye,
C. I. Modant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65;
C. I. Modant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, and 95;
C. I. Modant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, and 48;
C. I. Modant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, and 84;
C. I. Modant violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, and 58;
C. I. Dyes such as Modant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53.

The dyes exemplified above can be used alone or in combination of two or more.

The content of the dye is 0.5 to 80% by weight, preferably 0.5 to 60% by weight, more preferably 1 to 50% by weight based on the total weight of the colored photosensitive resin composition. When the content of the dye in the colorant is 0.5 to 80% by weight, it is possible to prevent the problem of the decrease in the reliability of the dye being eluted by the organic solvent after the pattern is formed, thereby increasing the sensitivity.

The content of the colorant is 5 to 60% by weight, preferably 10 to 45% by weight, based on the total weight of the colored photosensitive resin composition. When the colorant is contained in the range of 5 to 60% by weight, when a thin film is formed, the color density of the pixel is sufficient, and the non-pixel portion does not drop off at the time of development, and a residue hardly occurs.

In the present invention, the weight of the solid content in the colored photosensitive resin composition means the total weight of the remaining components excluding the solvent of the colored photosensitive resin composition.

(B) Alkali-soluble resin The alkali-soluble resin, which is one component of the colored photosensitive resin composition of the present invention, contains monomers represented by the following chemical formulas 1 and 2.

R _{1 to} R ₁₀ are the same or different and are each hydrogen or an alkyl group having 1 to 5 carbon atoms.

More preferably, R _{1 to} R ₁₀ are the same or different and each is hydrogen or a methyl group.

In the present invention, by using an alkali-soluble resin containing the monomers of the above-mentioned chemical formulas 1 and 2, it is possible to provide a colored photosensitive resin composition excellent in developability without developing stains.

Further, since the alkali-soluble resin has solubility in an alkali developing solution used in a developing process when a pattern is formed, an ethylenic resin containing a carboxyl group together with the monomers of the chemical formulas 1 and 2 is used. It is produced by copolymerizing the unsaturated monomer (b1) as an essential component.

Specific examples of the ethylenically unsaturated monomer (b1) containing 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; Anhydrides of dicarboxylic acids; mono (meth) acrylates of polymers containing carboxyl groups and hydroxyl groups at both terminals such as ω-carboxypolycaprolactone mono (meth) acrylate; and acrylic acid and methacrylic acid are preferred.

In addition, a hydroxyl group can be added to the alkali-soluble resin to secure additional developability.

As a method for providing the hydroxyl group, (1) a method of producing by copolymerizing an ethylenically unsaturated monomer containing a carboxyl group and an ethylenically unsaturated monomer containing a hydroxyl group; A method of producing by further reacting a compound containing a glycidyl group with a copolymer of an ethylenically unsaturated monomer containing a group, and (3) a method for preparing a compound containing an ethylenically unsaturated monomer containing a carboxyl group and a hydroxyl group. And a method in which a copolymer containing an ethylenically unsaturated monomer is additionally reacted with a compound containing a glycidyl group.

Specific examples of the hydroxyl group-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-3- Phenoxypropyl (meth) acrylate, N-hydroxyethyl acrylamide and the like, among which 2-hydroxyethyl (meth) acrylate is preferable, and the ethylenically unsaturated monomer containing a hydroxyl group is a combination of two or more. Can be used.

Specific examples of the compound containing a glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl Ether, benzyl glycidyl ether, glycidyl 4-tert-butyl benzoate, glycidyl stearate, aryl glycidyl ether, and glycidyl methacrylate, preferably butyl glycidyl ether, aryl glycidyl ether, and glycidyl methacrylate are preferred. The compounds containing a glycidyl group can be used in combination of two or more.

In the production of the alkali-soluble resin, the unsaturated monomer copolymerizable with the ethylenically unsaturated monomer containing a carboxyl group includes an aromatic vinyl compound, an N-substituted maleimide-based compound, ) Acrylates, hydroxyethyl (meth) acrylates, aryl (meth) acrylates, unsaturated oxetane compounds, and the like, but are not limited thereto.

The aromatic vinyl compound is specifically, for example, styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether , M-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

Specific examples of the N-substituted maleimide-based compound include, for example, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np -Hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np- Methoxyphenyl maleimide and the like.

Specifically, the alicyclic (meth) acrylates include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl ( Alkyl (meth) acrylates such as (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, and t-butyl (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- Methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decane-8-yl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate No.

The hydroxyethyl (meth) acrylates specifically include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3- Phenoxypropyl (meth) acrylate, N-hydroxyethylacrylamide, and the like.

Specific examples of the aryl (meth) acrylates include phenyl (meth) acrylate and benzyl (meth) acrylate.

The unsaturated oxetane compound is specifically, for example, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane , 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane.

The unsaturated monomers may be used alone or in combination of two or more.

The alkali-soluble resin may have an acid value of 60 to 120 mgKOH / g, preferably 70 to 100 mgKOH / g, in order to ensure compatibility with the dye and storage stability of the colored photosensitive resin composition. preferable.

When the acid value of the alkali-soluble resin is less than 60 mgKOH / g, it is difficult to secure a sufficient developing speed of the colored photosensitive resin composition. When the acid value exceeds 120 mgKOH / g, the adhesion between the colored photosensitive resin composition and the substrate is difficult. The short circuit of the pattern is likely to occur due to the decrease, the problem of compatibility with the dye occurs, the dye in the colored photosensitive resin composition precipitates, and the problem that the stability with time decreases and the viscosity increases. appear.

Further, the alkali-soluble resin preferably has a molecular weight of 12,000 to 17000, and more preferably has a molecular weight of 13000 to 15000.

If the molecular weight of the alkali-soluble resin is less than 12,000, short-circuiting of the pattern is likely to occur, and if it exceeds 17000, pattern residues are likely to occur.

The alkali-soluble resin is contained in an amount of 10 to 80% by weight, preferably 10 to 70% by weight, based on the total weight of the colored photosensitive resin composition.

When the content of the alkali-soluble resin is from 10 to 80% by weight, the solubility in a developing solution is sufficient and a pattern can be easily formed. The missing property of the part becomes good.

(C) Photopolymerizable compound The photopolymerizable compound, which is one of the colored photosensitive resin compositions of the present invention, must be a compound that can be polymerized by the action of a photopolymerization initiator (D) described below.

As the photopolymerizable compound, a monofunctional monomer, a bifunctional monomer, or a polyfunctional monomer can be used, and preferably, a bifunctional monomer is used, but is not limited thereto. Not something.

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. However, the present invention is not limited to these.

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, Examples include, but are not limited to, bis (acryloyloxyethyl) ether of bisphenol A, or 3-methylpentanediol di (meth) acrylate.

Specific examples of the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, or dipentaerythritol hexa (meth) acrylate Examples include, but are not limited to, acrylates.

The photopolymerizable compound is contained in an amount of 5 to 50% by weight, preferably 7 to 50% by weight, based on the total weight of the colored photosensitive resin composition of the present invention. The photopolymerizable compound can improve the strength and reliability of the pixel portion in the range of 5 to 50% by weight.

(D) Photopolymerization initiator The photopolymerization initiator, which is one of the colored photosensitive resin compositions of the present invention, is a compound that can polymerize the above-described photopolymerizable compound (C).

In the present invention, the photopolymerization initiator essentially contains an oxime ester fluorene derivative compound. By containing the oxime ester fluorene derivative compound, the sensitivity of the colored photosensitive resin composition is increased, and a high degree of curing can be exhibited.

Further, the photopolymerization initiator, from the viewpoint of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, etc., acetophenone-based compound, benzophenone-based compound, triazine-based compound, biimidazole-based compound, oxime compound, and thioxanthone-based It is preferable to additionally include one or more compounds selected from the group consisting of compounds.

The acetophenone-based compound is specifically, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1- [4- (2- Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and 2- (4- Methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like. .

Specific examples of the benzophenone-based compound include, for example, benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenylsulfide, 3,3 ′, 4,4′-tetra ( tert-butylperoxycarbonyl) benzophenone, and 2,4,6-trimethylbenzophenone.

Specifically, the triazine-based compound is, for example, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -(4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5- Triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-me Ruphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like. Can be

Specifically, the biimidazole-based compound is, for example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2, 3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4', 5 , 5'-Tetraphenyl-1,2'-biimidazole, and imidazole compounds in which the phenyl group at the 4,4 ', 5,5'-position is substituted by a carboalkoxy group. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5′-Tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole are preferably used.

The oxime compound specifically includes, for example, o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and commercially available products include OXE01 and OXE02 of Basff.

Specific examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

In addition, the photopolymerization initiator may further include a photopolymerization initiation aid (d1) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. Since the colored photosensitive resin composition according to the present invention contains the photopolymerization initiation assistant (d1), the sensitivity can be further increased and the productivity can be improved.

As the photopolymerization initiation aid, for example, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group can be preferably used.

As the amine compound, an aromatic amine compound is preferably used, and specifically, for example, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate; Ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethyl Amino) benzophenone (commonly called Michler's ketone), 4,4'-bis (diethylamino) benzophenone, and the like can be used.

As the carboxylic acid compound, it is preferable to use aromatic heteroacetic acids, and specifically, for example, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxy Examples include phenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, and 1,3,5-tris (3-mercaptobutyl). (Oxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) Pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate).

The photopolymerization initiator is contained in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total weight of the solid content in the colored photosensitive resin composition of the present invention.

When the photopolymerization initiator is contained in an amount of 0.1 to 40% by weight, the sensitivity of the colored photosensitive resin composition is increased, the exposure time is shortened, the productivity is improved, and high resolution can be maintained. Further, the strength of the pixel portion and the smoothness on the surface of the pixel portion are improved.

Further, the photopolymerization initiator is contained in an amount of 10 to 100% by weight, preferably 20 to 100% by weight, based on the total weight of the photopolymerization initiator.

If the photopolymerization initiation aid is contained in less than 10% by weight, the decrease in sensitivity due to the dye cannot be overcome, and a short circuit in the pattern is likely to occur during the development process.

(E) Solvent As long as the solvent is effective for dissolving other components contained in the colored photosensitive resin composition, a solvent used in a usual colored photosensitive resin composition is used without any particular limitation. In particular, ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters, or amides are preferable.

Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;
And diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether.

Examples of the acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, and 3-methyl-3-methoxy-1- Butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1-butyl acetate, 1,2-propylene glycol diacetate, ethylene Glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol Diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and the like.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, and 4-hydroxy-4-methyl-2-pentanone.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and γ-butyrolactone.

Examples of the amides include dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP).

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

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

The solvent is contained 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. When the solvent is contained in the range of 60 to 90% by weight, when applied by a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes called a die coater), and an inkjet, The property becomes good.

(F) Additives The additives can be selectively added as needed, and include, for example, other polymer compounds, curing agents, surfactants, adhesion promoters, ultraviolet absorbers, and aggregation prevention. One or more selected from the group consisting of agents can be included.

Specific examples of the other polymer compound include epoxy resins, curable resins such as maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and thermoplastic resins such as polyurethane. And the like.

The curing agent is used for deep curing and increasing mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

In the curing agent, specific examples of the epoxy compound include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, and other aromatic compounds. Epoxy resin, alicyclic epoxy resin, glycidyl ester resin, glycidylamine resin, or a brominated derivative of the epoxy resin, an aliphatic resin, an alicyclic or aromatic epoxy compound other than the epoxy resin and its brominated derivative Epoxidized butadiene (co) polymer, epoxidized isoprene (co) polymer, glycidyl (meth) acrylate (co) polymer, and triglycidyl isocyanurate.

In the curing agent, specific examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

The curing agent may be used together with the curing agent together with a curing auxiliary compound that enables ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound.

Examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic anhydrides, and acid generators. As the polyvalent carboxylic anhydrides, commercially available epoxy resin curing agents can be used. Examples of the commercially available products include Adeka Hardner EH-700 (manufactured by Adeka Industry Co., Ltd.), RIKACID HH (manufactured by Nippon Rika Co., Ltd.) and MH-700 (manufactured by Nippon Rika Co., Ltd.). The above-mentioned curing agents can be used alone or in combination of two or more.

The surfactant can be used to further improve the film formation of the colored photosensitive resin composition, and includes a silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric interface. Activators and the like are preferably used.

Examples of the silicone-based surfactant include commercially available products such as Dow Corning Toray Silicone's DC3PA, DC7PA, SH11PA, SH21PA, and SH8400, and GE Toshiba Silicone's TSF-4440, TSF-4300, and TSF-4445. , TSF-4446, TSF-4460, and TSF-4452.

Examples of the fluorine-based surfactant include commercially available products such as Megapis F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink and Chemicals, Inc.

Other commercially available products include KP (Shin-Etsu Chemical Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (Tochem Products), and MEGAFAC. (Dainippon Ink Chemical Industry Co., Ltd.), Flourd (Sumitomo 3M Limited), Asahi guard, Asahi Guard, Surflon (above, Asahi Glass Co., Ltd.), Solsperse (Lubrisol) , EFKA (EFKA Chemicals), PB821 (Ajinomoto Co.), Disperbyk-series (BYK-chemi), and the like.

The above-mentioned surfactants can be used alone or in combination of two or more.

The type of the adhesion promoter is not particularly limited, and specific examples of the adhesion promoter that can be used include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and N- (2-aminoethyl). ) -3-Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Propylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane Such as 3-isocyanate propyl trimethoxysilane and 3-isocyanate propyl triethoxysilane, and the like.

The above-mentioned adhesion promoters can be used alone or in combination of two or more. The adhesion promoter is usually contained in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of the solid content in the colored photosensitive resin composition.

The type of the ultraviolet absorber is not particularly limited, but specific examples that can be used include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone. Can be

The type of the aggregation preventing agent is not particularly limited, but specific examples that can be used include sodium polyacrylate.

The method for producing the colored photosensitive resin composition of the present invention is as follows.

First, the colorant (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle size of the pigment becomes about 0.2 μm or less. At this time, if necessary, a part or all of the pigment dispersant (a2) and the alkali-soluble resin (B) can be mixed with the solvent (E) to be dissolved or dispersed.

Add the remaining alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D), and if necessary, the additive (F) and the solvent (E) to the mixed colorant. The colored photosensitive resin composition according to the present invention can be produced by further adding it to a predetermined concentration.

The present invention also provides a color filter manufactured using the colored photosensitive resin composition and a display device including the same.

First, after applying the colored photosensitive resin composition on a substrate (usually glass) or a layer formed of the solid content of the previously formed colored photosensitive resin composition, by heating and drying, volatile components such as a solvent are removed. Remove to obtain a smooth coating.

As a coating method, for example, spin coating, cast coating, roll coating, slit and spin coating or slit coating can be used. After application, heating and drying (prebaking) or drying under reduced pressure are followed by heating to volatilize volatile components such as a solvent. Here, the heating temperature is usually 70 to 200 ° C, preferably 80 to 130 ° C. The thickness of the coating film after drying by heating is usually about 1 to 8 μm. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that the entire exposed portion is uniformly irradiated with the parallel light beam and accurate alignment between the mask and the substrate is performed. Irradiation with ultraviolet light cures the part irradiated with ultraviolet light.

As the ultraviolet light, g-ray (wavelength: 436 nm), h-ray, i-ray (wavelength: 365 nm) and the like can be used. The irradiation amount of the ultraviolet ray can be appropriately selected as needed, and is not limited in the present invention. When the cured coating film is brought into contact with a developing solution to dissolve and develop the non-exposed portions, a spacer having a desired pattern shape can be obtained.

The development method is not particularly limited to a liquid addition method, a dipping method, a spray method and the like. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound is not particularly limited to an inorganic or organic alkaline compound. 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 bicarbonate, potassium bicarbonate, sodium borate, potassium borate, and ammonia.

Examples of the organic alkaline compound include, for example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine And the like.

The inorganic or organic alkaline compounds can be used alone or in combination of two or more. The concentration of the alkaline compound in the developer is from 0.01 to 10% by weight, preferably from 0.03 to 5% by weight, based on the total weight of the developer.

As the surfactant in the developer, at least one selected from the group consisting of the above-described nonionic surfactants, anionic surfactants, and cationic surfactants can be used. The concentration of the surfactant in the developer is 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight based on the total weight of the developer. It is. After the development, the film may be washed with water, and if necessary, post-baked at 150 to 230 ° C. for 10 to 60 minutes.

Using the colored photosensitive resin composition of the present invention, a specific pattern can be formed on a substrate through the above-described steps.

Hereinafter, the present invention will be described in detail with reference to examples to specifically explain the present invention. However, embodiments according to the present invention can be modified in various different forms, and it should not be construed that the scope of the present invention is limited to the embodiments described in detail below. The embodiments of the present invention are provided to more completely explain the present invention to those having ordinary skill in the art.

<Synthesis of alkali-soluble resin>
Synthesis Examples 1 to 9.
A propylene glycol monomethyl ether acetate, AIBN, vinyl toluene, phenylthioethyl acrylate, methacrylate, and methacrylic acid were charged into a 1000 mL flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube. Replaced. Thereafter, the mixture was stirred, the temperature of the reaction solution was increased to 100 ° C., and after the increase, the reaction was performed for a certain period of time.

Content (parts by weight) of the composition and reaction time (h), final solid content (%) of the alkali-soluble resin synthesized by the method, acid value (KOH mg / g), and weight average molecular weight measured by GPC Are shown in Table 1 below.

Production Example 1. Production of pigment dispersion composition C.I. I. Pigment Green 58, 12 parts by weight, C.I. I. Pigment Yellow 150 1.8 parts by weight, BYK-2001 4 parts by weight as a pigment dispersing agent, and propylene glycol monomethyl ether acetate 82.2 parts by weight as a solvent are mixed, and the pigment is sufficiently dispersed using a bead mill. A composition was prepared.

<Production of colored photosensitive resin composition>
Examples 1-3 and Comparative Examples 1-8.
The colored photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 8 were produced with the compositions shown in Table 2 below.

Pigment dispersion composition: pigment dispersion composition produced in Production Example 1 alkali-soluble resin (B)
B1: Alkali-soluble resin produced in Synthesis Example 1 B2: Alkali-soluble resin B3 produced in Synthesis Example 2: Alkali-soluble resin B4 produced in Synthesis Example 3: Alkali-soluble resin B5 produced in Synthesis Example 4: Synthetic Example 5 Alkali-soluble resin B6 produced: Alkali-soluble resin B7 produced in Synthesis Example 6: Alkali-soluble resin B8 produced in Synthesis Example 7: Alkali-soluble resin B9 produced in Synthesis Example 8: Alkali-soluble resin produced in Synthesis Example 9 Polymerizable compound (C): A9550 (Shin-Nakamurasha)
Photopolymerization initiator (D):
D1: SPI-03 (Sanyosha)
D2: PBG-305 (TRONLY)
Solvent (E): propylene glycol monomethyl ether acetate

Experimental Example 1 Production of Color Filter and Measurement of Physical Properties Each of the colored photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 8 was spin-coated by a 2-inch glass substrate (manufactured by Corning Incorporated, "EAGLE XG"). ), And then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film.

After that, a photomask having a size of 3 cm × 3 cm and transmitting 100% was placed on the thin film, and irradiation with ultraviolet rays was performed at a distance of 200 μm from the test photomask. At this time, the ultraviolet ray was irradiated at an illuminance of 50 mJ / cm ² using a 1 kW high-pressure mercury lamp including all g, h and i rays, and no special optical filter was used.

1-1. Measurement of development stain The thin film irradiated with the ultraviolet rays was immersed in a 0.04% KOH aqueous solution development solution for 2 minutes and developed. In order to confirm the development stain, the post-process Bake was not advanced.

The film thickness of the color filter manufactured as described above was 2.5 μm.

Developed spots of the manufactured color filters were confirmed by Green Lamp.

The evaluation results are as follows, and the results are shown in Table 3 below.
<Evaluation criteria>
○: Excellent (Fig. 1)
Δ: good (FIG. 2)
×: defective (FIG. 3)

1-2. Measurement of Developing Property A 0.28 ml of a 0.008% aqueous KOH developing solution was dropped on the thin film which was not irradiated with the ultraviolet rays, and developed for 2 minutes. In order to confirm the development stain, the post-process Bake was not advanced.

The film thickness of the color filter manufactured as described above was 2.5 μm.

The developability of the manufactured color filter was confirmed with the naked eye.

The evaluation results are as follows, and the results are shown in Table 3 below.
<Evaluation criteria>
○: Excellent (Fig. 4)
×: defective (FIG. 5)

From the results in Table 3, the alkali-soluble resin containing the monomers of Chemical Formulas 1 and 2 and having a molecular weight of 12000 to 17000 and an acid value of 60 to 120 KOH mg / g, and an oxime ester as a photopolymerization initiator It was confirmed that the colored photosensitive resin composition of the present invention using the fluorene derivative compound did not cause development stains and was excellent in developability.

On the other hand, the colored photosensitive resin compositions of Comparative Examples 1 to 6 in which the acid value and the molecular weight of the alkali-soluble resin do not fall within the scope of the present invention exhibited development stains and poor developability.

Further, the colored photosensitive resin compositions of Comparative Examples 7 and 8 in which the oxime ester fluorene derivative compound was not used as the photopolymerization initiator had good developability, but showed a large number of development stains.

Therefore, it was found through experiments that the colored photosensitive resin composition of the present invention did not cause development stains and was excellent in developability.

Claims (6)

Coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a colored photosensitive resin composition containing a solvent,
The alkali-soluble resin is produced by copolymerizing monomers of the following chemical formulas 1 and 2,
The molecular weight of the alkali-soluble resin is 12000 to 17000, the acid value is 60 to 120 KOHmg / g,
A colored photosensitive resin composition, wherein the photopolymerization initiator contains an oxime ester fluorene derivative compound.

(In the formula, each of R _{1 to} R ₁₀ is the same or different and is hydrogen or an alkyl group having 1 to 5 carbon atoms.) The colored photosensitive material according to claim 1, wherein the alkali-soluble resin is produced by copolymerizing the monomers of the formulas (1) and (2); and an ethylenically unsaturated monomer having a carboxyl group. Resin composition. 2. The colored photosensitive resin composition according to claim 1, wherein R _{1 to} R _{10 in} Formula 1 and Formula 2 are the same or different and each is hydrogen or a methyl group. 3. 5 to 60% by weight of a coloring agent, 10 to 80% by weight of an alkali-soluble resin, 5 to 50% by weight of a photopolymerizable compound, and 0. 1% by weight based on the total weight of solid components in the colored photosensitive resin composition. The colored photosensitive resin composition according to claim 1, comprising 1 to 40% by weight, and 60 to 90% by weight of a solvent based on the total weight of the colored photosensitive resin composition. A color filter produced from the colored photosensitive resin composition according to claim 1. A display device comprising the color filter according to claim 5.

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