KR20230125637A - Colored Photosensitive Resin Composition, Color Filter and Display Device - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition comprising: a colorant; an alkali-soluble resin; a photopolymerizable compound; a photopolymerization initiator; and a solvent, wherein the photopolymerizable compound includes a tetra-functional or higher (meth)acrylic monomer of 10 to 50 wt% to which 45 or more ethylene oxides of a specific structure are added with respect to 100 wt% of the total photopolymerizable compound, to a color filter formed using the same, and to an image display device equipped with the color filter. The colored photosensitive resin composition according to the present invention has excellent adhesion when forming ultra-high resolution patterns, and no residue on a lower substrate or development stains occur.

Description

Colored photosensitive resin composition, color filter and image display device {Colored Photosensitive Resin Composition, Color Filter and Display Device}

The present invention relates to a colored photosensitive resin composition, a color filter, and an image display device, and more particularly, to a colored photosensitive resin composition that has excellent adhesion when forming ultra-high resolution patterns and does not generate lower substrate residues and development stains, and formed using the same It relates to a color filter and an image display device having the color filter.

Color filters are widely used in plasma display panels (PDPs), liquid crystal displays (LCDs), field emission displays (FELs) and light emitting displays (LEDs), and their application range is rapidly expanding. In particular, the color filter is recognized as one of the most important components in reproducing the color tone of the LCD.

In recent years, the pixel size of color filters has been gradually reduced to realize ultra-high resolution image quality. Accordingly, there is a demand for a colored photosensitive resin composition that has excellent adhesion even when forming ultra-fine patterns and does not generate lower substrate residues and development stains.

Conventionally, as a photopolymerizable compound, for example, dipentaerythritol hexaacrylate (hereinafter referred to as DPHA) has been used to form a color filter for a liquid crystal display (LCD), and conventionally, only DPHA containing composition was used. However, when only DPHA is used, there is a problem in that a composition to be removed by an alkaline developer remains on the substrate as a residue during development when ultrafine patterns are formed.

In particular, this problem is more serious when developing by a puddle method for reducing developer and securing uniformity over a large area.

On the other hand, Korean Patent Publication No. 10-2009-0072754 discloses a composition for a color filter including a pigment and a binder resin, but there is a problem in that the pattern characteristics are poor when forming an ultra-high resolution pattern.

Republic of Korea Patent Publication No. 10-2009-0072754

One object of the present invention is to provide a colored photosensitive resin composition that has excellent adhesion when forming ultra-high resolution patterns and does not generate residues on a lower substrate and stains from development.

Another object of the present invention is to provide a color filter formed using the colored photosensitive resin composition.

Another object of the present invention is to provide an image display device having the color filter.

On the other hand, the present invention is a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

The photopolymerizable compound includes a tetrafunctional or higher functional (meth)acrylic monomer to which ethylene oxide represented by Formula 1 is added in an amount of 10 to 50% by weight based on 100% by weight of the total photopolymerizable compound. Provide a colored photosensitive resin composition do.

[Formula 1]

In the above formula,

X is an aliphatic hydrocarbon group having 1 to 10 carbon atoms with or without oxygen or hetero atoms, or A;

R ¹ is oxygen or an aliphatic hydrocarbon group having 1 to 10 carbon atoms with or without a hetero atom;

R ² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms with or without a hetero atom;

A is is,

R ³ is hydrogen or a methyl group;

EO is an ethylene oxide group,

n is an integer from 1 to 4;

m is an integer from 45 to 96;

In one embodiment of the present invention, the photopolymerizable compound may further include a trifunctional or higher functional (meth)acrylic monomer.

In one embodiment of the present invention, the trifunctional or more (meth)acrylic monomer may be included in an amount of 50 to 90% by weight based on 100% by weight of the total photopolymerizable compound.

In one embodiment of the present invention, the photopolymerizable compound may be included in an amount of 5 to 80% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition.

In one embodiment of the present invention, the photopolymerization initiator may include an oxime-based photopolymerization initiator.

On the other hand, the present invention provides a color filter formed using the colored photosensitive resin composition.

On the other hand, the present invention provides an image display device characterized in that the color filter is provided.

The colored photosensitive resin composition according to the present invention contains, as a photopolymerizable compound, a tetrafunctional or higher-functional (meth)acrylic monomer to which 45 or more ethylene oxides of a specific structure are added in a specific content range, and thus has excellent adhesion and prevents residues and development stains on the lower substrate. It does not occur, so it has excellent developability even if it goes through a puddle-type developing process to form an ultra-high resolution pattern.

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

One embodiment of the present invention comprises a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), wherein the photopolymerizable compound (C) has a specific structure It relates to a colored photosensitive resin composition comprising a tetrafunctional or higher functional (meth)acrylic monomer to which 45 or more ethylene oxides are added in an amount of 10 to 50% by weight based on 100% by weight of the total photopolymerizable compound.

Colorant (A)

In one embodiment of the present invention, the colorant (A) includes a pigment (a1) and/or a dye (a2).

pigment (a1)

As the pigment, organic or inorganic pigments generally used in the art may be used.

As the organic pigment, various pigments used in printing ink, inkjet ink, etc. may be used. Specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, Perylene pigment, perinone pigment, dioxazine pigment, anthraquinone pigment, dianthraquinonyl pigment, anthrapyrimidine pigment, anthanthrone pigment, indanthrone pigment, pravanthrone pigment, pyranthrone ) pigments, diketopyrrolopyrrole pigments, and the like.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides or composite metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. oxide; Carbon black etc. are mentioned.

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

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185

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

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 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.

The above 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. A pigment selected from Pigment Green 58 can be preferably used.

These can be used individually or in combination of 2 or more types, respectively.

It is preferable to use a pigment dispersion in which the particle size is uniformly dispersed as the pigment. As an example of a method for uniformly dispersing the particle size of the pigment, a method of dispersing treatment by containing a pigment dispersant (a3) may be mentioned. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained. there is.

Pigment Dispersant (a3)

The pigment dispersant (a3) is added to maintain the deagglomeration and stability of the pigment, and specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants. These can be used individually or in combination of 2 or more types, respectively.

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

As the pigment dispersant (a3), other resin-type pigment dispersants may be used in addition to the above acrylate-based dispersants. The other resin-type pigment dispersants include known resin-type pigment dispersants, particularly polycarboxylic acid esters represented by polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, and (partial) polycarboxylic acids. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) an oily dispersant such as an amide formed by reaction of a polyester having a carboxyl group with a poly(lower alkyleneimine) or a salt thereof; water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; modified polyacrylate; adducts of ethylene oxide/propylene oxide and phosphate esters; and the like.

Commercially available resin type dispersants are cationic resin dispersants, for example, trade names of BYK (Big) Chemistry: 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 brand names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names of Lubrizol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Trade names of Kawaken Fine Chemical Co.: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Trade names of Ajinomoto: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Trade names of Kyoeisha Chemical Co., Ltd.: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44 and the like.

In addition to the above 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 content of the pigment dispersant (a3) is 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the pigment (a1). If the content of the pigment dispersant (a3) exceeds 60 parts by weight, the viscosity may increase, and if it is less than 5 parts by weight, it may be difficult to fine-partize the pigment or may cause problems such as gelation after dispersion.

Dye (a2)

The dye (a2) may be used without limitation as long as it has solubility in organic solvents. Preferably, it is preferable to use a dye capable of securing reliability such as solubility in an alkaline developing solution, heat resistance, and solvent resistance while having solubility in organic solvents.

As the dye, acid dyes having an acidic group such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamide-based acid dyes, and derivatives thereof may be used. In addition, azo-based, xanthene-based, and phthalocyanine Acid dyes of the system and their derivatives can also be selected.

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

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

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

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

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

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

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

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

Among them, C.I. Among solvent dyes, C.I. Solvent Yellow 14, 16, 21, 56, 79, 93, 151; 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, 70; C.I. Solvent violet 13 is preferred, and among them, C.I. Solvent Yellow 21, 79; C.I. Solvent Red 8, 122, 132; C.I. Solvent Orange 45 and 62 are more preferred.

Also, C.I. As an acid dye,

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 1 84, yellow dyes such as 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

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, 3 49, red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 426;

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

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

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

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

Among the acid dyes, C.I. Acid Yellow 42; C.I. Acid Red 52, 92; C.I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27 is preferred.

In addition, as a C.I. direct dye,

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

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

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

C.I. Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 1 89, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 2 48, blue dyes such as 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

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

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

Also, C.I. As a modanto dye,

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

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

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

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

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

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

In the present invention, the dye (a2) may be used alone or in combination of two or more.

The colorant (A) may be included in an amount of 5 to 60% by weight, preferably 10 to 45% by weight, based on 100% by weight of the total solid content in the colored photosensitive resin composition. When the content of the colorant (A) is within the above range, there is an advantage in that color concentration of pixels is sufficient when thin film is formed, and no residue is generated because omission of non-pixel parts is not deteriorated during development.

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

Alkali-soluble resin (B)

In one embodiment of the present invention, the alkali-soluble resin (B) usually has reactivity and alkali solubility by the action of light or heat, and acts as a dispersion medium for a coloring material.

The alkali-soluble resin (B) is preferably prepared by copolymerizing an ethylenically unsaturated monomer (b1) having a carboxyl group.

Specific examples of the ethylenically unsaturated monomer (b1) having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; anhydrides of these dicarboxylic acids; and mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as omega-carboxypolycaprolactone mono(meth)acrylate. Among these, acrylic acid and methacrylic acid are preferable.

The alkali-soluble resin (B) may be provided with a hydroxyl group to secure additional developability.

In order to impart a hydroxyl group to the alkali-soluble resin (B), it may be prepared by copolymerizing an ethylenically unsaturated monomer (b1) having a carboxyl group and an ethylenically unsaturated monomer (b2) having a hydroxyl group, and an ethylenically unsaturated monomer (b1) having a carboxyl group It can be prepared by further reacting the compound (b3) having a glycidyl group with the copolymer of ). It can also be produced by reacting a compound (b3) having a glycidyl group with a copolymer of an ethylenically unsaturated monomer (b1) having a carboxyl group and an ethylenically unsaturated monomer (b2) having a hydroxyl group.

Specific examples of the ethylenically unsaturated monomer (b2) having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, Hydroxy-3-phenoxypropyl (meth)acrylate, N-hydroxyethyl acrylamide, etc., among which 2-hydroxyethyl (meth)acrylate is preferable, and the ethylenically unsaturated monomer having a hydroxyl group described above (b2) can be used in combination of 2 or more types.

Specific examples of the compound (b3) having 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-t-butyl benzoate, glycidyl stearate, allyl glycidyl ether, methacrylic acid glycidyl ester, etc., and among them, butyl glycidyl ether, allyl glycidyl ether, and methacrylic acid glycidyl ester are preferred, and the compounds (b3) having a glycidyl group described above are two The above can be used in combination.

In addition, in addition to the ethylenically unsaturated monomer (b2) having a hydroxyl group and the compound (b3) having a glycidyl group in the ethylenically unsaturated monomer (b1) having a carboxyl group during the preparation of the alkali-soluble resin (B), a copolymerizable unsaturated monomer (b4) may be copolymerized.

Specific examples of the copolymerizable unsaturated monomer (b4) include,

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

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

Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, Alkyl (meth)acrylates, such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate;

Cyclopentyl(meth)acrylate, cyclohexyl(meth)acrylate, 2-methylcyclohexyl(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl(meth)acrylate, 2- alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate;

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

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

The monomers exemplified as the copolymerizable unsaturated monomer (b4) may be used alone or in combination of two or more.

The preparation method of the copolymer is not particularly limited, and conventionally known polymerization methods may be used, and solution polymerization is preferred among known polymerization methods. In addition, the polymerization temperature or polymerization time varies depending on the type or ratio of the monomers to be introduced, the molecular weight and acid value of the desired alkali-soluble resin, but may be polymerized at, for example, 60 to 130° C. for 1 to 10 hours.

In the case of using a solvent during the polymerization, a solvent used in a conventional radical polymerization reaction may be used, specifically, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone , methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl Ether, toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide and the like can be used. These solvents can be used individually or in combination of 2 or more types.

As the polymerization initiator used during the polymerization, a commonly used polymerization initiator may be added, and is not particularly limited. Specifically, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate, t-butyl organic peroxides such as peroxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), etc. Nitrogen compounds are mentioned. These can be used individually or in combination of 2 or more types.

During the polymerization, a chain transfer agent may be used to control the molecular weight or molecular weight distribution of the copolymer. Examples of the chain transfer agent include mercapto compounds such as n-dodecanethiol, mercaptoacetic acid, and methyl mercaptoacetate; α-methylstyrene dimer and the like can be used.

The acid value of the alkali-soluble resin (B) is preferably 30 to 150 mgKOH/g. The acid value here is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the polymer, and can usually be obtained by titrating using an aqueous potassium hydroxide solution. If the acid value of the alkali-soluble resin (B) is less than 30 mgKOH/g, it is difficult to secure a sufficient development rate for the colored photosensitive resin composition, and if it exceeds 150 mgKOH/g, the adhesion with the substrate is reduced, and short circuit of the pattern is likely to occur, and the dye A compatibility problem occurs, and the dye in the colored photosensitive resin composition is precipitated, or the storage stability of the colored photosensitive resin composition is lowered, and the viscosity is likely to increase.

In addition, the weight average molecular weight in terms of polystyrene (hereinafter simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; using tetrahydrofuran as an elution solvent) is 5,000 to 50,000, preferably 5,000 to 30,000. Alkali-soluble resins are preferred. When the weight average molecular weight of the alkali-soluble resin (B) is in the above range, the coating film hardness is improved, the film remaining rate is high, the solubility in the developing solution of the unexposed area is good, and the resolution tends to improve, so it is preferable.

The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the alkali-soluble resin (B) is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of 1.5 to 6.0 is preferable because developability is excellent.

The alkali-soluble resin (B) may be included in an amount of 10 to 80% by weight, preferably 10 to 70% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition. When the alkali-soluble resin (B) is included in the above range, the solubility in the developing solution is sufficient to facilitate pattern formation, and the film reduction of the pixel portion of the exposed area is prevented during development, so that the omission of the non-pixel portion is good It is desirable because

Photopolymerizable Compound (C)

In one embodiment of the present invention, the photopolymerizable compound (C) is a compound that can be polymerized by the action of the photopolymerization initiator (D), and is a tetrafunctional or higher-functional (meth)acryl with 45 or more ethylene oxides having a specific structure added thereto. contains monomers;

The tetrafunctional or higher functional (meth)acrylic monomer to which 45 or more ethylene oxides are added is a compound represented by the following formula (1).

[Formula 1]

In the above formula,

X is an aliphatic hydrocarbon group having 1 to 10 carbon atoms with or without oxygen or hetero atoms, or A;

R ¹ is oxygen or an aliphatic hydrocarbon group having 1 to 10 carbon atoms with or without a hetero atom;

R ² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms with or without a hetero atom;

A is is,

R ³ is hydrogen or a methyl group;

EO is an ethylene oxide group,

n is an integer from 1 to 4;

m is an integer from 45 to 96;

In one embodiment of the present invention, X may be oxygen, alkylene having 1 to 10 carbon atoms, oxyalkylene having 1 to 10 carbon atoms, or A, particularly oxygen or A.

In one embodiment of the present invention, R ¹ may be oxygen, an alkylene having 1 to 10 carbon atoms, or an oxyalkylene having 1 to 10 carbon atoms, particularly a methylene group.

In one embodiment of the present invention, R ² is an alkylene having 1 to 10 carbon atoms or an oxyalkylene having 1 to 10 carbon atoms, and may be particularly a methylene group.

In one embodiment of the present invention, m may be an integer from 45 to 96 as described above. When m is an integer less than 45, developability may be deteriorated or residue may be generated when forming an ultra-high resolution pattern, and when m is an integer greater than 96, adhesion may be insufficient and pattern tearing may occur.

Commercially available products of the ethylene oxide-added tetrafunctional (meth)acrylic multifunctional monomer represented by Formula 1 include A-DPH-48E and A-DPH-96E manufactured by Shin Nakamura.

The ethylene oxide-added tetrafunctional or higher (meth)acrylic multifunctional monomer represented by Formula 1 may be included in an amount of 10 to 50% by weight, preferably 20 to 40% by weight, based on 100% by weight of the total photopolymerizable compound. there is. If the content of the ethylene oxide-added polyfunctional (meth)acrylic monomer represented by Chemical Formula 1 is less than the above range, residue may be generated due to lack of developability when forming ultra-high resolution patterns, and if it exceeds the above range, ultra high resolution Pattern tearing may occur due to lack of adhesion during pattern formation.

In one embodiment of the present invention, the photopolymerizable compound may further include a trifunctional or higher functional (meth)acrylic monomer. The trifunctional or higher functional (meth)acrylic monomer may be a trifunctional to hexafunctional (meth)acrylic monomer.

For example, the trifunctional or higher functional (meth)acrylic monomer includes trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and propoxylated trimethylolpropane tri(meth)acrylate. Acrylates, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, pro Poxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, but the like, but is not limited thereto.

The trifunctional or higher (meth)acrylic monomer may be included in an amount of 50 to 90% by weight, preferably 60 to 80% by weight, based on 100% by weight of the total photopolymerizable compound. If the content of the trifunctional or higher (meth)acrylic monomer is less than 50% by weight, pattern tearing may occur due to lack of adhesion when forming an ultra-high resolution pattern. can happen

In one embodiment of the present invention, the photopolymerizable compound is 5 to 80% by weight, preferably 20 to 60% by weight, more preferably 30 to 50% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition. may be included in quantity. When the photopolymerizable compound is included in the above range, strength or smoothness of the pixel portion may be good, and pattern characteristics may be good when forming an ultra-high resolution pattern.

Photopolymerization initiator (D)

In one embodiment of the present invention, as long as the photopolymerization initiator (D) can polymerize the photopolymerizable compound (C), the type thereof may be used without particular limitation. The photopolymerization initiator (D) is an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, an oxime-based compound, and a thioctic compound from the viewpoint of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, etc. It is preferable to use at least one compound selected from the group consisting of santhone-based compounds, and in particular, it is preferable to use an oxime-based compound in terms of pattern characteristics when forming ultra-high resolution patterns.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyl) Roxyethoxy) 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, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra ( tert-butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro). Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole , 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl)-4, 4'5,5'-tetraphenyl-1,2'-biimidazole or a biimidazole compound in which the phenyl group at the 4,4',5,5' position is substituted with a carboalkoxy group; and the like. Among 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 do.

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

The oxime-based compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), ethanone 1-[9-ethyl-6-(2-methyl Benzoyl) -9H carbazol-3-yl] -1- (O-acetyl oxime), etc. Commercially available products include TR-PBG-305 (TRONLY), OXE-01 (BASF), OXE-02 (BASF) g), etc.

Examples of the thioxanthone-based compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. there is

In addition, the photopolymerization initiator (D) may be used in combination with a photopolymerization initiator (d1) in order to improve the sensitivity of the colored photosensitive resin composition for green pixels of the present invention. The colored photosensitive resin composition for green pixels according to the present invention contains the photopolymerization initiation auxiliary agent (d1), so that the sensitivity is further increased and productivity can be improved.

As the photopolymerization initiation aid (d1), for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group may be preferably used.

Specific examples of the amine compound include aliphatic amine compounds 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, Aromatic amine compounds such as 4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone) and 4,4'-bis(diethylamino)benzophenone may be used, and it is particularly preferable to use an aromatic amine compound. do.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenyl Thioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptobutyrate) ), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. there is.

The photopolymerization initiator (D) may be included in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C). When the photopolymerization initiator (D) is included in the above range, the colored photosensitive resin composition of the present invention is highly sensitive and the exposure time is shortened, which is preferable because productivity is improved and high resolution can be maintained. In addition, the strength of the pixel portion formed using the composition under the above-described conditions and the smoothness of the surface of the pixel portion may be improved.

Further, when the photopolymerization initiation auxiliary agent (d1) is further used, the photopolymerization initiation auxiliary agent (d1) is 0.1 to 40 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C). , Preferably it may be included in an amount of 1 to 30 parts by weight. When the photopolymerization initiation aid (d1) is included within the above range, the sensitivity of the colored photosensitive resin composition may be further increased, and productivity of a color filter formed using the composition may be improved.

Solvent (E)

In one embodiment of the present invention, as long as the solvent (E) is effective in dissolving other components included in the colored photosensitive resin composition, solvents used in conventional colored photosensitive resin compositions may be used without particular limitation, particularly ether. hydrocarbons, aromatic hydrocarbons, ketones, alcohols, esters or amides are preferred.

Specifically, the solvent (E) includes ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; Aromatic hydrocarbons, such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; Cyclic esters, such as esters, such as 3-ethoxy ethyl propionate and 3-methoxy methyl propionate, and (gamma)-butyrolactone, etc. are mentioned.

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

In one embodiment of the present invention, the solvent (E) may be included in an amount of 60 to 90% by weight, preferably 65 to 85% by weight based on 100% by weight of the entire colored photosensitive resin composition. When the solvent (E) is contained within the above range, coating properties are improved when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as a die coater), inkjet, or the like. can

Additive (F)

Colored photosensitive resin composition according to an embodiment of the present invention, in addition to the above components, fillers, other polymer compounds, curing agents, surfactants, adhesion promoters, ultraviolet absorbers, and aggregation inhibitors according to the needs of those skilled in the art within the range that does not impair the object of the present invention It is also possible to use additives (F) such as these together.

Specifically, glass, silica, alumina, etc. may be used as the filler, but is not limited thereto.

Examples of the other polymer compounds include thermosetting resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, and polyurethanes. It may, but is not limited thereto.

The curing agent is used to increase deep curing and mechanical strength, and specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. may be used, but is not limited thereto. The epoxy compound is specifically, bisphenol A-based epoxy resin, hydrogenated bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, hydrogenated bisphenol F-based epoxy resin, novolac-type epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, Glycidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co)polymer epoxides, isoprene (co-) ) Polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, etc. may be used, but is not limited thereto. Specifically, the oxetane compound may be carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexane dicarboxylic acid bisoxetane, etc., but are limited thereto It is not.

The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of an epoxy group of an epoxy compound and an oxetane skeleton of an oxetane compound together with the curing agent. Specifically, polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, acid generators, and the like may be used as the curing auxiliary compound. The polyhydric carboxylic acid anhydrides may be commercially available as epoxy resin curing agents. Examples of the commercially available epoxy resin curing agent include a trade name (Adeka Hadona EH-700) (manufactured by Adeka Kogyo Co., Ltd.), a trade name (Rika Siddo HH) (manufactured by Shinnippon Ewha Co., Ltd.), and a trade name (MH-700). (manufactured by Shin Nippon Ewha Co., Ltd.); and the like.

The curing agent and curing auxiliary compound exemplified above may be used alone or in combination of two or more.

The surfactant may be used to further improve the film formation of the colored photosensitive resin composition of the present invention, and fluorine-based surfactants, silicone-based surfactants, and the like may be preferably used.

The silicone-based surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 of Dow Corning Toray Silicon as commercial products, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, and TSF-4440 of GE Toshiba Silicone. 4460, TSF-4452, etc. The fluorine-based surfactants include, for example, Megafac F-470, F-471, F-475, F-482, F-489, F-554 and the like of Dainippon Ink and Chemicals Co., Ltd. as commercial products.

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

The adhesion promoter is specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane, 3-isocyanate propyltrimethoxysilane and 3-isocyanate propyltriethoxysilane may be used alone or in mixtures thereof.

The adhesion promoter may be included in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition.

Specifically, the ultraviolet absorber may be 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, etc., but is not limited thereto.

The aggregation inhibitor may specifically use sodium polyacrylate or the like, but is not limited thereto.

The colored photosensitive resin composition according to an embodiment of the present invention can be prepared, for example, by the following method.

First, the pigment (a1) of the colorant (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, if necessary, the pigment dispersant (a3), some or all of the alkali-soluble resin (B), or the dye (a2) may be mixed with the solvent (E) to be dissolved or dispersed. The remainder of the alkali-soluble resin (B), a photopolymerization initiator (D), a photopolymerizable compound (C), an additive (F), and, if necessary, a solvent (E) are further added to the mixed dispersion to a predetermined concentration, according to the present invention. A colored photosensitive resin composition according to can be prepared.

One embodiment of the present invention relates to a color filter formed using the colored photosensitive resin composition described above. A color filter according to an embodiment of the present invention is characterized in that it includes a colored layer formed by applying the above-described colored photosensitive resin composition on a substrate and exposing and developing in a predetermined pattern.

Hereinafter, the pattern formation method using the colored photosensitive resin composition of the present invention will be described in detail.

A method for forming a pattern using the colored photosensitive resin composition of the present invention may use a method known in the art, but typically includes an application step; exposure step; and a removal step. By applying the colored photosensitive resin composition of the present invention on a substrate, photocuring and developing to form a pattern, it can be used as a colored pixel (colored image).

Specifically, the colored photosensitive resin composition is applied on a glass substrate to which nothing is coated or a glass substrate to which SiNx (protective film) is applied to a thickness of 500 to 1,500 Å using an appropriate method such as spin coating or slit coating, It is applied in a thickness of 3.4 μm. After application, light is irradiated to form a pattern required for the color filter. After light is irradiated, when the coating layer is treated with an alkaline developer, the unirradiated portion of the coating layer is dissolved and a pattern required for the color filter is formed. By repeating this process according to the required number of R, G, and B colors, a color filter having a desired pattern can be obtained. In addition, in the above process, crack resistance, solvent resistance, and the like can be further improved by heating the image pattern obtained by development again or curing by irradiation with actinic rays or the like.

One embodiment of the present invention relates to an image display device provided with the color filter described above.

The color filter of the present invention is used for various image displays such as not only a conventional liquid crystal display (LCD) but also an electroluminescence display (EL), a plasma display (PDP), a field emission display (FED), and an organic light emitting diode (OLED). applicable to the device.

The image display device of the present invention includes a configuration known in the art, except for having the color filter described above.

Hereinafter, the present invention will be described in more detail by Examples, Comparative Examples and Experimental Examples. These Examples, Comparative Examples and Experimental Examples are only for explaining the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not limited thereto.

Preparation Example 1: Preparation of Pigment Dispersion A-1

C.I. Pigment Blue 15:6 12.0 parts by weight, C.I. 1.8 parts by weight of Acid Red 52, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate were mixed and mixed and dispersed in a bead mill for 12 hours to prepare a pigment dispersion A-1.

Synthesis Example 1: Synthesis of alkali-soluble resin (B-1)

In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 19 parts by weight of acrylic acid, benzyl meth After adding 10 parts by weight of acrylate, 51 parts by weight of styrene, and 3 parts by weight of n-dodecylmercaptan, nitrogen substitution was performed. Thereafter, while stirring, the temperature was raised to 110° C. and reacted for 6 hours. Subsequently, after lowering the temperature of the reaction solution to room temperature and replacing the air in the flask with normal air again, 0.3 parts by weight of triethylamine and 20 parts by weight of glycidyl methacrylate were added and reacted at 110 ° C. for 5 hours to obtain an alkali-soluble resin. prepared (60% by weight of solids). The solid acid value of the alkali-soluble resin thus synthesized was 80 mgKOH/g, and the weight average molecular weight (Mw) measured by GPC was about 22,000.

Examples 1 to 6 and Comparative Examples 1 to 6: Preparation of colored photosensitive resin composition

A colored photosensitive resin composition was prepared by mixing each component according to the composition shown in Table 1 below (unit: parts by weight).

Example comparative example One 2 3 4 5 6 One 2 3 4 5 6 (A) colorant A-1 35 35 35 35 35 35 35 35 35 35 35 35 (B) alkali soluble resin B-1 22 22 22 22 22 22 22 22 22 22 22 22 (C) photopolymerizable compound C-1 8.4 8.4 9.5 7.5 12 11 4 8.4 C-2 8.4 8.4 C-3 3.6 3.6 2.5 4.5 12 One 8 3.6 C-4 3.6 3.6 C-5 3.6 C-6 8.4 (D) photopolymerization initiator D-1 One One One One One One One One One One One One (E) Solvent E-1 30 30 30 30 30 30 30 30 30 30 30 30

A-1: Pigment dispersion of Preparation Example 1

B-1: Alkali-soluble resin of Synthesis Example 1

C-1: trimethylolpropane triacrylate (trifunctional (meth)acrylic monomer, A-TMPT, Shin Nakamura)

C-2: dipentaerythritol hexaacrylate (hexafunctional (meth)acrylic monomer, A-9550, Shin Nakamura)

C-3: In Formula 1, m is 48 compound (hexafunctional, A-DPH-48E, Shin Nakamura)

C-4: In Formula 1, m is 96 compound (hexafunctional, A-DPH-96E, Shin Nakamura)

C-5: In Formula 1, m is 24 compound (hexafunctional, A-DPH-24E, Shin Nakamura)

C-6: 1,6-hexanediol diacrylate (A-HD-N, Shin-Nakamura)

D-1: Ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9Hcarbazol-3-yl]-1-(O-acetyloxime) (Irgacure OXE-02, manufactured by BASF)

E-1: propylene glycol monomethyl ether acetate

Experimental Example 1

A color filter was prepared as follows using the colored photosensitive resin composition prepared in the above Examples and Comparative Examples, and the physical properties at this time were measured in the following manner, and the results are shown in Table 2 below.

<Manufacture of color filter>

The colored photosensitive resin composition was applied on a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100° C. for 3 minutes to form a thin film. Subsequently, a test photomask having a line/space pattern of 1 μm to 10 μm was placed on the thin film and ultraviolet rays were irradiated. At this time, the ultraviolet light source was irradiated at 100 mJ/cm 2 using a 1KW high-pressure mercury lamp containing all of g, h, and i rays, and no special optical filter was used. The thin film irradiated with ultraviolet rays was developed in a puddle method using a KOH aqueous solution developing solution having a pH of 10.5. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230° C. for 5 minutes to prepare a color filter.

(1) Adhesion

When the generated pattern was evaluated through an optical microscope, the degree of tearing on the pattern was evaluated according to the following evaluation criteria.

<Evaluation Criteria>

○: No tearing in the pattern

△: 1 to 5 tears in the pattern

×: More than 5 tears in the pattern

(2) Substrate residue

When the non-patterned portion of the generated color filter was evaluated through an optical microscope, the degree of undevelopment on the lower substrate was evaluated according to the following evaluation criteria.

<Evaluation Criteria>

○: no residue

△: Residue present in part of the lower base material

×: Residue present on the entire lower base material

(3) development stain

Distilled water was dropped on the substrate, left at room temperature for 2 minutes, and then dried by blowing nitrogen gas. Subsequently, Na lamp was irradiated on the substrate and the surface state of the coating film was observed to visually determine whether or not stains occurred, and developed stains were evaluated according to the following evaluation criteria.

<Evaluation Criteria>

○: Circular water stains are not recognized on the surface of the coating film

△: Fine circular water stains were recognized on the surface of the coating film

×: Water stains are clearly recognized on the surface of the coating film

adhesion Subbase Residue developing stain Example One ○ ○ ○ 2 ○ ○ ○ 3 ○ ○ ○ 4 ○ ○ ○ 5 ○ ○ ○ 6 ○ ○ ○ comparative example One ○ × × 2 × ○ ○ 3 ○ × Δ 4 × ○ ○ 5 ○ × Δ 6 × ○ ○

As shown in Table 2, 10 to 50% by weight of a tetrafunctional or higher (meth)acrylic monomer to which 45 or more ethylene oxides of a specific structure are added as a photopolymerizable compound according to the present invention, based on 100% by weight of the total photopolymerizable compound It was confirmed that the colored photosensitive resin compositions of Examples 1 to 6 containing the amount of had excellent adhesion during formation of ultra-fine patterns, and did not generate residues on the lower substrate and development stains.

On the other hand, the colored photosensitive resin compositions of Comparative Examples 1 to 5 that do not contain a tetrafunctional or higher (meth)acrylic monomer to which 45 or more ethylene oxides of a specific structure are added or are outside the above content range have poor adhesion when forming ultrafine patterns. Alternatively, it was confirmed that residues of the lower substrate and/or developing stains were generated. On the other hand, the colored photosensitive resin composition of Comparative Example 6 using a less than trifunctional (meth)acrylic monomer was found to have insufficient adhesiveness, resulting in pattern tearing.

Having described specific parts of the present invention in detail above, it is clear that these specific techniques are only preferred embodiments for those skilled in the art to which the present invention belongs, and the scope of the present invention is not limited thereto. do. Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above information.

Accordingly, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

Claims (7)

A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,
The photopolymerizable compound is a colored photosensitive resin composition comprising an amount of 10 to 50% by weight based on 100% by weight of the total photopolymerizable compound of a tetrafunctional or higher functional (meth)acrylic monomer to which ethylene oxide is added represented by Formula 1:
[Formula 1]

In the above formula,
X is an aliphatic hydrocarbon group having 1 to 10 carbon atoms with or without oxygen or hetero atoms, or A;
R ¹ is oxygen or an aliphatic hydrocarbon group having 1 to 10 carbon atoms with or without a hetero atom;
R ² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms with or without a hetero atom;
A is is,
R ³ is hydrogen or a methyl group;
EO is an ethylene oxide group,
n is an integer from 1 to 4;
m is an integer from 45 to 96; The colored photosensitive resin composition according to claim 1, wherein the photopolymerizable compound further comprises a trifunctional or higher (meth)acrylic monomer. The colored photosensitive resin composition according to claim 2, wherein the trifunctional or higher (meth)acrylic monomer is included in an amount of 50 to 90% by weight based on 100% by weight of the total photopolymerizable compound. The colored photosensitive resin composition according to claim 1, wherein the photopolymerizable compound is included in an amount of 5 to 80% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition. The colored photosensitive resin composition according to claim 1, wherein the photopolymerization initiator comprises an oxime-based photopolymerization initiator. A color filter formed using the colored photosensitive resin composition according to any one of claims 1 to 5. An image display device characterized in that the color filter according to claim 6 is provided.