KR101689058B1 - Colored photosensitive resin composition and color filter using the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, and more particularly, to a colored photosensitive resin composition for a color filter used for producing a color filter used in a color liquid crystal display device or the like, and a color filter manufactured using the same. The colored photosensitive resin composition of the present invention exhibits high sensitivity even under pixel formation conditions with a low exposure dose and is characterized in that surface defects such as muffle phenomenon caused by fins do not occur in the production of color filters.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition and a color filter using the colored photosensitive resin composition.

The present invention relates to a colored photosensitive resin composition, and more particularly, to a colored photosensitive resin composition for a color filter used for producing a color filter used in a color liquid crystal display device or the like, and a color filter manufactured using the same.

BACKGROUND ART [0002] Color filters are widely used in imaging devices, liquid crystal display devices, and the like, and their application range is rapidly expanding. A color filter used for a color liquid crystal display device, an image pickup device, or the like is a device for uniformly applying a colored photosensitive resin composition containing a coloring agent corresponding to each color of red, green and blue on a substrate on which a black matrix is pattern- The coating film formed by heating and drying (hereinafter also referred to as preliminary firing) may be exposed and developed, and if necessary, further heat curing (hereinafter also referred to as post-firing) may be repeated for each color, Color pixels are formed.

On the other hand, in the manufacturing process of the color filter, a stain-like mura phenomenon occurs on the substrate. The mura phenomenon refers to a phenomenon in which irregular luminance over the whole or a part of the panel due to errors, It is said that stains appearing characteristic are generated.

In this connection, the conventional photosensitive resin composition has been actively studied for improving the solvent resistance, heat resistance, developing speed, etc., but still has problems such as sensitivity problems and generation of toner image due to fins in the production of color filters. For example, Korean Patent Laid-Open No. 10-2005-0076606 discloses a photosensitive resin composition having an average vapor pressure of less than 3.0 mmHg at 20 DEG C of a solvent, Korean Patent Publication No. 10-2008-0096472 discloses a photosensitive resin composition having a boiling point of 100 to 200 And a solvent having a boiling point of 150 to 330 DEG C, but only a solution of the boiling point of the solvent or the restoration of the color filter is described, and a solution for suppressing the generation of mura I do not propose.

Korean Patent Publication No. 10-2005-0076606 Korean Patent Publication No. 10-2008-0096472

Accordingly, it is an object of the present invention to provide a photosensitive resin composition which has a high sensitivity characteristic and does not cause a pinhole phenomenon in manufacturing a color filter.

(A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), wherein the colored photosensitive resin composition Wherein the solvent (E) has a vapor pressure such that the value of PMI (Pin No Index Index) is 3 or less in the following formula (1).

[Equation 1]

PMI = -35.6139 + 25.82603 * Vapor pressure of solvent - 5.18984 * (Vapor pressure of solvent) ² + 0.324966 * (Vapor pressure of solvent) ³

An embodiment of the present invention may be such that the PMI is defined by the following equation (2).

&Quot; (2) "

PMI = | (the color of the plate portion - (the color of the pin portion)) | x 1000

In Equation (2), the plate portion refers to a portion where no pin is present in the substrate during vacuum drying in the manufacture of a color filter, and the pin portion refers to a portion where the pin exists.

In another embodiment, the colored photosensitive resin composition may be such that no pinhole phenomenon occurs in manufacturing a color filter.

In another embodiment, the colorant (A) is contained in an amount of 5 to 60 wt%, the alkali-soluble resin (B) is contained in an amount of 5 to 85 wt%, the photopolymerizable material (C) And the photopolymerization initiator (D) comprises 0.1 to 40% by weight based on the total solid weight of the alkali-soluble resin (B) and the photopolymerizable compound (C) May be contained in an amount of 60 to 90% by weight based on the total weight of the colored photosensitive resin composition.

Another embodiment may further comprise an additive (F).

The present invention also provides a color filter made of the colored photosensitive resin composition.

The colored photosensitive resin composition of the present invention is characterized in that surface defects such as mura phenomenon caused by fins are not generated in the production of a color filter.

1 is a graph showing a correlation between a PMI (Pin Mura Index) and a vapor pressure of a solvent according to Equation 1 described in the embodiment.

Hereinafter, the present invention will be described in detail.

The colored photosensitive resin composition comprises a colorant (A), an alkali soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E) Wherein the photosensitive resin composition has a vapor pressure such that the PMI (Pin No Index Index) value is 3 or less in Equation (1).

[Equation 1]

PMI = -35.6139 + 25.82603 * Vapor pressure of solvent - 5.18984 * (Vapor pressure of solvent) ² + 0.324966 * (Vapor pressure of solvent) ³

A mura phenomenon occurs in the form of a speckle pattern on the substrate during the color filter manufacturing process. The mura phenomenon refers to a phenomenon in which irregular luminance characteristics over the whole or a part of the panel due to errors or manufacturing failures in the color filter manufacturing process Refers to the occurrence of the speckles indicated. There is a pin in a VCD (Vacuum Dry) apparatus, and a color difference occurs between a portion where the pin exists on the substrate and a portion where the pin does not exist, and the color difference is recognized by the color difference.

The present invention has experimentally confirmed that the vapor pressure of the solvent contained in the colored photosensitive resin composition has the relationship of PMI with the above formula (1), thereby completing the present invention.

The PMI is a numerical value defined by the following equation (2) as a mura phenomenon caused by a pin during vacuum drying.

&Quot; (2) "

PMI = | (the color of the plate portion - (the color of the pin portion)) | x 1000

In Equation (2), the plate portion refers to a portion where no pin exists in the substrate during vacuum drying in the production of a color filter, and the pin portion refers to a portion where the pin exists.

The color is defined as follows and can be obtained by measuring with a colorimeter.

Red: R _x

Green: G _y

Blue: B _y

For example, in the case of Red, the PMI can be calculated by substituting the color of the flat portion obtained through the colorimeter and the color of the fin portion into Equation 2 above.

When the PMI value is less than 3, no mura phenomenon occurs. Accordingly, by controlling the vapor pressure of the solvent using Equation (1), it is possible to manufacture a photosensitive resin composition that minimizes pinning due to a low PMI value.

Hereinafter, each configuration will be described in more detail.

The colorant (A)

The colorant (A) may contain at least one kind of pigment (a1) as an essential component and optionally contain at least one kind of dye (a2). Further, it may preferably contain a pigment dispersant (a3).

Pigment ( a1 )

The pigment may be an organic pigment or an inorganic pigment generally used in the art.

The organic pigments may be various pigments used in printing ink, ink jet ink, etc. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, An anthanthrone pigment, an indanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, a pyranthrone pigment, A pyranthrone pigment, a diketopyrrolopyrrole pigment, and the like.

Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts. Specific examples of the inorganic pigments include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Or composite metal oxides.

Particularly, the organic pigments and inorganic pigments may be specifically classified into pigments in the Society of Dyers and Colourists, and more specifically, those having a color index (CI) number Pigments, but are not limited thereto.

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

C.I Pigment Black 1 and 7, etc.

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

The exemplified C.I. Among the pigment pigments, 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, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. Pigment Green 58 may be preferably used.

It is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment includes a method of dispersing the pigment dispersion (a3) by containing the pigment dispersant (a3). According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained have.

The content of the pigment (a1) is in the range of 10 to 50% by weight, preferably 15 to 45% by weight, based on the total solid content in the pigment dispersion composition. When the content of the pigment is in the range of 15 to 40% by weight, the viscosity is low, the storage stability is excellent, and the dispersion efficiency is high, which is effective for increasing the contrast ratio.

Pigment dispersant ( a3 )

The pigment dispersant (a3) is added for maintenance of deagglomeration and stability of the pigment, and any of those generally used in the art can be used without limitation. Specific examples of the pigment dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, and polyamine surfactants. These surfactants may be used singly or in combination of two or more thereof . (Hereinafter referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate). At this time, it is preferable to apply the acrylic dispersant prepared by a living control method as disclosed in Korean Patent Laid-Open Publication No. 2004-0014311. DISCLOSURE OF INVENTION It is an object of the present invention to provide an acrylic dispersant, 2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.

The acrylic dispersants exemplified above may be used alone or in combination of two or more.

As the pigment dispersant (a3), other resin type pigment dispersants other than the acrylic dispersant may be used.

The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) An amine salt of a polycarboxylic acid, an alkylamine salt of a polycarboxylic acid, a polysiloxane, a long chain polyaminoamide phosphate salt, an ester of a hydroxyl group-containing polycarboxylic acid and a modified product thereof, Oil dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters.

DISPER BYK-161, DISPER BYK-162, DISPER BYK-163 and DISPER BYK-160 available from BYK (Big) Chemie are commercially available as the above-mentioned resin type pigment dispersant. BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co.,

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

The amount of the pigment dispersant (a3) to be used is in the range of 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (a1). If the content of the pigment dispersant (a3) exceeds 60 parts by weight, the viscosity may be increased. If the content of the pigment dispersant is less than 5 parts by weight, it may be difficult to atomize the pigment or cause gelation after dispersion.

dyes( a2 )

The dye can be used without limitation as long as it has solubility in an organic solvent. It is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility in an alkali developing solution, heat resistance and solvent resistance.

Examples of the dye include acid dyes having an acidic group such as a sulfonic acid and a carboxylic acid, salts of an acidic dye and a nitrogen-containing compound, sulfonamides of an acidic dye and derivatives thereof, and azo, xanthate, phthalocyanine Based acid dyes and derivatives thereof.

Preferably, the dye is a compound classified as a dye in a color index (published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (coloring yarn).

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

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

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

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

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

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

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

C.I. Solvent dye having excellent solubility in an organic solvent. Solvent Yellow 14, 16, 21, 56, 151, 79, 93; C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Orange 41, 45, 62; C.I. Solvent Blue 35, 36, 44, 45, 70; C.I. Solvent violet 13 is preferred, and C.I. Solvent Yellow 21, 79; C.I. Solvent Red 8, 122, 132; C.I. Solvent orange 45, 62 is more preferable.

Also, C.I. As an acid dye

CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 Yellow dyes such as 1,1,1,2,2,2,2,2,2,23,28, 240,242, 243,251 and the like, such as, for example, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, ;

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

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;

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

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

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

CI Acid Yellow 42, which is excellent in solubility in organic solvents in acid dyes; C.I. Acid Red 92; C. I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27 is preferred.

As a C.I. direct dye,

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

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

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

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

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

Also, C.I. As a modantoic dye

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

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

CI Modanato Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, dyes;

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

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

Green dyes such as C.I. Modatto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43,

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

The content of the dye in the colorant (A) is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, particularly preferably 1 to 50% by weight, based on the total weight of the solid content of the colorant (A) Do. When the content of the dye in the colorant (A) is within the above range, it is possible to prevent the problem of lowering the reliability of dye elution by the organic solvent after forming the pattern, and it is preferable since the sensitivity is excellent.

The content of the colorant (A) is 5 to 60% by weight, preferably 10 to 45% by weight, based on the total solid weight of the colored photosensitive resin composition. When the colorant (A) is contained in an amount of 5 to 60% by weight based on the above standard, the color density of the pixel is sufficient even when a thin film is formed, and the residue of the non- Do.

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

The alkali-soluble resin (B)

In the present invention, the alkali-soluble resin may be an acrylic copolymer that is soluble in the solvent of the present invention and has reactivity to the action of light or heat, functions as a binder resin for the colorant and is soluble in an alkaline developer, Can be used without particular limitation.

Examples of the acrylic copolymer include a copolymer of a carboxyl group-containing monomer and other monomer copolymerizable with the monomer.

Specific examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids or unsaturated polycarboxylic acids having at least one carboxyl group in the molecule such as unsaturated dicarboxylic acid and unsaturated tricarboxylic acid. .

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like.

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like.

The unsaturated polycarboxylic acid may be its mono (2-methacryloyloxyalkyl) ester, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) Phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate and the like. .

These carboxyl group-containing monomers may be used alone or in combination of two or more.

Specific examples of the other monomers copolymerizable with the carboxyl group-containing monomer include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o- P-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, Aromatic vinyl compounds such as vinylbenzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Acrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Acrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene Acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxy Acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, unsaturated carboxylic acid esters such as glycerol monoacrylate, glycerol monomethacrylate; Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane having a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain Macromers and the like.

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

The content of the carboxyl group-containing monomer units in the alkali-soluble resin may be 10 to 50% by weight, preferably 15 to 40% by weight, and more preferably 25 to 40% by weight based on the total monomer content. When the content of the carboxyl group-containing monomer unit is 10 to 50% by weight, the solubility in the developer is good and the pattern tends to be accurately formed at the time of development.

Examples of the acrylic copolymer include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2- (Meth) acrylate / benzyl (meth) acrylate copolymer, a (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, a (Meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (Meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, 2-hydroxyethyl (meth) acrylate / benzyl Acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxy Acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer / styrene / benzyl (Meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer. Here, (meth) acrylate means acrylate or methacrylate.

Of these, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl / Methyl (meth) acrylate / styrene copolymer is preferably used.

The weight average molecular weight of the alkali-soluble resin in terms of polystyrene may be generally from 5,000 to 50,000, preferably from 8,000 to 40,000, more preferably from 10,000 to 35,000, and most preferably from 10,000 to 30,000. When the molecular weight of the alkali-soluble resin is 5,000 to 50,000, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the unexposed portion in the developing solution is good, and the resolution tends to be improved.

The acid value of the alkali-soluble resin is usually 50 to 150, preferably 60 to 140, more preferably 80 to 135, and most preferably 80 to 130. When the acid value is from 50 to 150, the solubility in a developing solution is improved, the unexposed portion is easily dissolved, and the high sensitivity is obtained, so that the pattern of the exposed portion tends to remain and the residual film ratio tends to be improved. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.

The alkali-soluble resin may be contained in an amount of 5 to 85% by weight, preferably 10 to 70% by weight, based on the total solid content of the colored photosensitive resin composition of the present invention. When the alkali-soluble resin is contained in an amount of 5 to 85% by weight based on the above-mentioned criteria, solubility in a developing solution is sufficient, so that development residue does not easily occur on the substrate of the non-pixel region, It is difficult to generate and the dropout of non-pixel regions tends to be favorable.

Photopolymerization  The compound (C)

In the present invention, the photopolymerizable compound is a compound that can be polymerized by an active radical, acid, or the like generated from a photopolymerization initiator by irradiation of light. In the present specification, the term "photopolymerizable compound" means a monomer having at least one functional group and is described as a monofunctional, bifunctional, or bifunctional polymerizable compound depending on the number of functional groups.

Specific examples of the monofunctional polymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, Pyrrolidone and the like.

Specific examples of the bifunctional polymerizable compound include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol di ) Acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylate Neopentyl glycol diacrylate, propyloxylate neopentyl glycol diacrylate, and the like.

Specific examples of the triblock polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylate trimethylolpropane tri (meth) acrylate, propyloxylate trimethylolpropane tri (Meth) acrylate, glyceryl propyloxytriacrylate, isocyanurate triarylate, and the like.

Specific examples of the tetrafunctional polymerizable compound include pentaerythritol tetra (meth) acrylate, dimethylol propane tetra (methyl) acrylate, and the like.

Specific examples of the pentafunctional polymerizable compound include dipentaerythritol penta (meth) acrylate, and specific examples of the hexafunctional photopolymerizable compound include dipentaerythritol hexa (meth) acrylate.

Among them, a bifunctional or higher functional polyfunctional polymerizable compound can be preferably used, and a bifunctional or higher functional polyfunctional polymerizable compound is most preferably used.

The photopolymerizable compound (C) is preferably contained in an amount of 5 to 50% by weight, and more preferably 7 to 45% by weight based on the total weight of solid components in the colored photosensitive resin composition. When the photopolymerizable compound (C) is contained in an amount of 5 to 50% by weight based on the above-mentioned criteria, the strength and smoothness of the pixel portion tends to be favorable.

Light curing Initiator (D)

In the present invention, the photopolymerization initiator can be used without any particular limitation as long as it can polymerize the alkali-soluble resin and the photopolymerizable compound. In particular, from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price, it is preferable to use an acetophenone, benzoin, benzophenone, thioxanthone, triazine, oxime, And a benzoin tosylate-based compound, and a light stabilizer may be used in combination. The photopolymerization initiator may be divided into an active radical generator which generates an active radical upon irradiation with light, a sensitizer, an acid generator, and the like.

Examples of the active radical generator include benzoin, acetophenone, benzophenone, thioxanthone, triazine, and oxime compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan- Phenylpropane-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) Oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan- Methylthiophenyl) propan-1-one are more preferable. The acetophenone-based compounds may be used alone or in combination of two or more, and may be used in combination with other photopolymerization initiators.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Specific examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'- Butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propanedioxanthone, and the like.

Specific examples of triazine compounds include 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- (4- methoxystyryl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- (Trichloromethyl) -6- [2- (4-diethylamino-2- (trifluoromethyl) Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4- dimethoxyphenyl) ethenyl] -1,3,5- Triazine, and the like.

Specific examples of the oxime compounds include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (4-methylsulfanyl-phenyl) -butan-1-one oxime-O-acetate, hydroxyimino- -Acetic acid ethyl ester-O-acetate, and hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-benzoate.

Specific examples of the sensitizer include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl- Benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, and the like can be given. have.

Specific examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate , 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfonate, di Onium salts such as phenyl iodonium hexafluoroantimonate, and nitrobenzyl tosylates, benzoin tosylates and the like. Among the above compounds, for example, there are compounds which simultaneously generate an active radical and an acid such as a triazine-based compound.

The photopolymerization initiator may be contained in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total weight of solids of the alkali-soluble resin and the photopolymerizable compound of the present invention. When the photopolymerization initiator is included as the above-mentioned standard, the colored photosensitive resin composition is highly sensitized and the exposure time is shortened, so that productivity is improved and high resolution can be maintained.

In the present invention, a photopolymerization initiator may be further added together with a photopolymerization initiator. The photopolymerization initiator is used in combination with a photopolymerization initiator and is used to promote polymerization of the photopolymerizable compound initiated by the photopolymerization initiator. Examples of the photopolymerization initiator include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and the like.

Specific examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, (Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dimethylamino) benzophenone, Bis (ethylmethylamino) benzophenone, and 4,4'-bis (diethylamino) benzophenone are preferable.

Specific examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, .

Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- -Propoxyloxanthone, and the like.

The photopolymerization initiator may be used alone or in combination of two or more. A commercially available product, EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Specific examples of the combination of the preferred photopolymerization initiator and the photopolymerization initiator are diethoxyacetophenone and 4,4'-bis (diethylamino) benzophenone; 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and 4,4'-bis (diethylamino) benzophenone; 2-hydroxy-2-methyl-phenylpropan-1-one and 4,4'-bis (diethylamino) benzophenone; 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one and 4,4'-bis (diethylamino) benzophenone; 1-hydroxycyclohexyl phenyl ketone and 4,4'-bis (diethylamino) benzophenone; Oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one and 4,4'-bis (diethylamino) benzophenone; A combination of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 4,4'-bis (diethylamino) benzophenone, Methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and 4,4'-bis (diethylamino) benzophenone.

When the photopolymerization initiator and the photopolymerization initiator are used together, the content of the photopolymerization initiator is preferably 10 mol or less, more preferably 0.01 to 5 mol based on 1 mol of the photopolymerization initiator. When the photopolymerization initiator is contained in an amount of 10 mol or less based on 1 mol of the photopolymerization initiator, the sensitivity of the colored photosensitive resin composition is higher and the productivity of the color filter formed by using the composition tends to be improved.

Solvent (E)

In the present invention, the solvent is not particularly limited as long as it is effective for dispersing or dissolving the other components contained in the colored photosensitive resin composition. The solvent may be selected from esters, aromatic hydrocarbons, ketones, alcohols, Drew and the like are preferable.

Specific examples of the ethers include tetrahydrofuran, tetrahydropyrane, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol mono Methyl ethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol methyl ether, propylene Propyleneglycol monomethyl ether acetate, propyleneglycol monopropyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propyleneglycol methyl ether acetate, methoxy Butylacetate And the like can be given site, methoxy pentyl acetate, anisole, phenetole or methyl anisole.

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

Specific examples of the ketone include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone or cyclohexanone.

Specific examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

Specific examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, alkyl esters, Methyl methoxyacetate, methyl methoxyacetate, methyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3- Ethyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- Methyl propionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- But are not limited to, methyl ethyl ketone, ethyl methyl ketone, ethyl methyl ketone, ethyl methyl ketone, ethyl methyl ketone, ethyl methyl ketone, ethyl methyl ketone, ethyl methyl ketone, ethyl methyl ketone, And lactones.

Specific examples of amides include N, N-dimethylformamide or N, N-dimethylacetamide.

Examples of other solvents include N-methylpyrrolidone and dimethylsulfoxide.

Preferably, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate or propylene glycol methyl ether are used alone or in combination of two or more.

The solvent may be 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 it is contained in the above-mentioned amounts, when it is coated with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (or a "die coater") or an inkjet, desirable.

Additive (F)

The additive (F) may be optionally added, for example, other polymer compounds, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an antiflocculant.

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

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

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides and isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

Specific examples of the oxetane compound in the curing agent include carbonates bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like.

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. The curing assistant compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agent include epoxy resin curing agents such as epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, Manufactured by Japan Ehwa Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

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

Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 from Dow Corning Toray Silicone Co., Ltd. and TSF-4440, TSF-4300, TSF-4445, TSF-4446 and TSF-4460 , And TSF-4452. Examples of the fluorine-based surfactant include Megafox (registered trademark) F-470, F-471, F-475, F-482, F-489 and F-554 manufactured by Dainippon Ink and Chemicals, Incorporated. The above-exemplified surfactants may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, methacryloxypropyltrimethoxysilane, and the like. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the solid content of the colored photosensitive resin composition.

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

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

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

The process for producing the colored photosensitive resin composition of the present invention will be described as follows.

First, the colorant is mixed with a solvent and dispersed using a bead mill or the like until the average particle diameter of the colorant becomes about 0.2 μm or less. At this time, if necessary, it may be mixed with a part or all of the pigment dispersant and the alkali-soluble resin to dissolve or disperse it.

The remainder of the alkali-soluble resin, the photopolymerizable compound, and the photopolymerization initiator and, if necessary, the additional solvent are added to the mixed dispersion (hereinafter, also referred to as "mill base") at a predetermined concentration, A photosensitive resin composition can be prepared.

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. However, the following examples, comparative examples and experimental examples are for illustrating the present invention, and the present invention is not limited by the following examples, comparative examples and experimental examples, and can be variously modified and changed. In the following Examples and Comparative Examples, "%" and "part" representing the content are based on weight unless otherwise specified.

Example  1 to 4 and Comparative Example  1 to 9

A colored photosensitive resin composition was prepared as shown in Table 1 so that the vapor pressure of the solvent was controlled.

(단위: 중량%)

(Unit: wt%)

The components in Table 1 are as follows.

(A-1) Colorant: C.I. Pigment Red 254

(B-1) Alkali-soluble resin: copolymer of methacrylic acid and benzylmethacrylate as an alkali-soluble resin (the molar ratio of methacrylic acid unit to benzylmethacrylate unit was 27:73, acid value was 83, weight average molecular weight was 18,000 )

(C-1) Photopolymerizable compound: dipentaerythritol hexaacrylate

(D-1) Photopolymerization initiator: 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-

(D-2) Photopolymerization initiator: 4,4'-bis (diethylamino) benzophenone

(D-3) Photopolymerization initiator: 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl]

(E-1) Additive: Megafox (registered trademark) F554 (manufactured by Dainippon Ink and Chemicals, Inc.)

(E-2) Additive: methacryloxypropyltrimethoxysilane as adhesion promoter

(F-1) Solvent: ethyl 3-ethoxypropionate

(F-2) Solvent: 1-methoxy-2-propanol

(F-3) Solvent: Propylene glycol diacetate

(F-4) Solvent: propylene glycol monomethyl ether acetate

Experimental Example  1. Mura phenomenon measurement by pin

The colored photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 9 were applied to a glass substrate ("EAGLE XG", manufactured by Corning Incorporated) with a spin coater method on a 2 inch square glass substrate and vacuum dried Dry), then placed on a heating plate and maintained at a temperature of 100 ° C for 3 minutes to form a color layer thin film. Then, a test photomask having a pattern changing stepwise in the range of 1 to 100% transmittance and a line / space pattern of 1 to 50 m was placed on the color layer thin film, And irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated at a light intensity of 100 mJ / cm 2 using a 1 kW high pressure mercury lamp containing g, h and i lines, and no special optical filter was used. The color layer thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes for development. The glass substrate on which the developed color layer thin film was formed was washed with distilled water, dried in a nitrogen gas atmosphere, and heated for 1 hour in a heating oven at 200 ° C to thermally cure the color filter. The thickness of the color layer of the manufactured color filter was 1.8 mu m.

The PMI (pin index index) defined by the following equation (2) and the pinhole phenomenon were measured for the obtained color filter, and the results are shown in Table 2 below.

Also, the relationship between the PMI and the vapor pressure of the solvent was analyzed (Fig. 1), and the following equation (1) was derived.

[Equation 1]

PMI = -35.6139 + 25.82603 * Vapor pressure of solvent - 5.18984 * (Vapor pressure of solvent) ² + 0.324966 * (Vapor pressure of solvent) ³

[PMI (Pin Mura Index Index)]

The muffling phenomenon caused by the pin during vacuum drying is expressed by the following equation (2).

&Quot; (2) "

PMI = | (the color of the plate portion - (the color of the pin portion)) | x 1000

In Equation (2), the plate portion refers to a portion where no pin exists in the substrate during vacuum drying in the production of a color filter, and the pin portion refers to a portion where the pin exists.

The colors are defined as follows and measured with a colorimeter.

Red: R _x

Green: G _y

Blue: B _y

division Phenomenon caused by pin PMI Example 1 X 2.25 Example 2 X 2.17 Example 3 X 2.99 Example 4 X 2.19 Comparative Example 1 ○ 5.36 Comparative Example 2 ○ 3.04 Comparative Example 3 ○ 4.53 Comparative Example 4 ○ 5.25 Compare to 5 ○ 5.28 Comparative Example 6 ○ 5.37 Comparative Example 7 ○ 3.69 Comparative Example 8 ○ 5.3 Comparative Example 9 ○ 3.33

○: Magnetic phenomenon occurs due to pin

X: no pinning phenomenon occurs

As shown in Table 2, it was confirmed that when PMI calculated by Equation (1) is 3 or less, pinning does not occur.

Claims (6)

(A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E)
Wherein the solvent (E) has a vapor pressure so that the value of PMI (Pin No Index index) in the following formula (1) is 3 or less,
The PMI is defined by the following equation (2)
Wherein the colored photosensitive resin composition does not cause a pinhole phenomenon during the production of a color filter;
[Equation 1]
PMI = -35.6139 + 25.82603 * Vapor pressure of solvent - 5.18984 * (vapor pressure of solvent) ² + 0.324966 * (vapor pressure of solvent) ³ ;
&Quot; (2) "
PMI = | (the color of the plate portion - (the color of the pin portion)) | x 1000
In Equation (2), the plate portion refers to a portion where there is no pin in the substrate during vacuum drying in the manufacture of a color filter, and the pin portion refers to a portion where the pin exists. delete delete The method according to claim 1,
The colored photosensitive resin composition contains, based on the total solid weight,
The colorant (A) is contained in an amount of 5 to 60% by weight,
The alkali-soluble resin (B) comprises 5 to 85% by weight,
The photopolymerizable material (C) is contained in an amount of 5 to 50% by weight,
The photopolymerization initiator (D) is contained in an amount of 0.1 to 40% by weight based on the total solid weight of the alkali-soluble resin (B) and the photopolymerizable compound (C)
Wherein the solvent (E) is contained in an amount of 60 to 90% by weight based on the total weight of the colored photosensitive resin composition. The method according to claim 1,
Wherein the colored photosensitive resin composition further comprises an additive (F). A color filter made of a colored photosensitive resin composition according to any one of claims 1 to 5.

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