KR102349141B1 - Colored photo sensitive resin composition, a color filter comprising the same, and a display devide comprising the color filter - Google Patents

Abstract

상기 화학식 1에서 n은 0 내지 10의 정수이다.
[화학식 2]

상기 화학식 2에서,
A는 CH 또는 질소이고,
R₁ 내지 R₈은 각각 독립적으로 수소, 알킬기, 하기 화학식 3, -COR₁₆ 또는 -NO₂인 것이며, R₁₆은 아릴기이고,
R₁₃은 알킬기, 알케닐기, 시클로알케닐기, 알키닐기, 시클로알킬기 또는 아릴기이다.
[화학식 3]

상기 화학식 3에서,
상기 R₁₄는 수소, 시클로알킬기, 알케닐기, 알콕시기, 알킬기 또는 아릴기이고, 상기 R₁₅는 아릴기, 헤테로아릴기이고, 또는 알킬기이고, 상기 X는 -CO- 또는 직접 연결이고, *는 결합손이다.The present invention includes (A) a colorant, (B) an alkali-soluble resin, (C) a thermosetting resin represented by Formula 1 below, (D) a photopolymerizable compound, (E) a photopolymerization initiator, and (F) a solvent, (A) the colorant includes Pigment Red 179, Pigment Red 208, and carbon black, and the (E) photopolymerization initiator includes a compound represented by the following Chemical Formula 2, and a colored photosensitive resin composition using the same Provided are a manufactured color filter, and a display device including the color filter.
[Formula 1]

In Formula 1, n is an integer of 0 to 10.
[Formula 2]

In Formula 2,
A is CH or nitrogen,
R ₁ to R ₈ are each independently hydrogen, an alkyl group, Formula 3 below, -COR ₁₆ or -NO ₂ , R ₁₆ is an aryl group,
R ₁₃ is an alkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkyl group, or an aryl group.
[Formula 3]

In Formula 3,
Wherein R ₁₄ is hydrogen, a cycloalkyl group, an alkenyl group, an alkoxy group, an alkyl group or an aryl group, wherein R ₁₅ is an aryl group, a heteroaryl group, or an alkyl group, wherein X is -CO- or a direct connection, and * is is a bonding hand.

Description

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

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

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

The coloring pattern of each of the color filters is generally formed using a colored photosensitive resin composition including a colorant such as a pigment or dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The coloring pattern processing using the colored photosensitive resin composition is generally performed by a lithography process.

Colored photosensitive resins are essential materials for color filters, liquid crystal display materials, organic light emitting devices, displays, and the like. For example, in a color filter of a color liquid crystal display, a light blocking layer using a black photosensitive composition is formed at the boundary between the colored layers in order to enhance the contrast and color effect of red, green, and blue. In addition, recently, it is required to be positioned on an array substrate to not only serve as a black matrix, but also to form a spacer for maintaining a cell gap so that various roles can be performed at once. Accordingly, not only an optical effect for basic light blocking, but also characteristics of good elasticity and reliability are required.

Republic of Korea Patent No. 10-1648607 discloses a technique for improving the contrast ratio of the ink composition to improve the characteristics of a color filter manufactured using the ink composition and a display device including the color filter, but characteristics limited to red It provides an improvement, and there is a problem in that reliability is lowered during low-temperature curing, making it difficult to apply to various processes.

Republic of Korea Patent Registration No. 10-1648607

An object of the present invention is to provide a colored photosensitive resin composition having improved properties such as solvent resistance and adhesiveness by having excellent curing degree even when curing at a low temperature to improve the above-described prior art problems.

Another object of the present invention is to prevent deterioration of color characteristics of a device including a thin film manufactured by using the colored photosensitive resin composition.

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

In addition, the present invention using the colored photosensitive resin composition, the spectral transmittance is 10% or less at 580 nm or less, 70% or less at 580 nm to 630 nm, 60% to 90% at 630 nm to 780 nm To provide a color filter included in the range aim to

In order to achieve the above object, the present invention, (A) a colorant, (B) an alkali-soluble resin, (C) a thermosetting resin represented by the following formula (1), (D) a photopolymerizable compound, (E) a photopolymerization initiator and ( F) including a solvent, wherein the (A) colorant includes Pigment Red 179, Pigment Red 208 and carbon black, and the (E) photopolymerization initiator includes a compound represented by the following Chemical Formula 2 A colored photosensitive resin composition is provided.

[Formula 1]

In Formula 1, n is an integer of 0 to 10.

[Formula 2]

In Formula 2,

A is CH or nitrogen,

R ₁ to R ₈ are each independently hydrogen, an alkyl group, Formula 3 below, -COR ₁₆ or -NO ₂ , R ₁₆ is an aryl group,

R ₁₃ is an alkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkyl group, or an aryl group.

[Formula 3]

In Formula 3,

Wherein R ₁₄ is hydrogen, a cycloalkyl group, an alkenyl group, an alkoxy group, an alkyl group or an aryl group, wherein R ₁₅ is an aryl group, a heteroaryl group, or an alkyl group, wherein X is -CO- or a direct connection, and * is is a bonding hand.

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

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

The colored photosensitive resin composition of the present invention includes a photopolymerization initiator including a thermosetting resin represented by Formula 1 and a compound represented by Formula 2, and thus has excellent curing degree even when cured at low temperatures, solvent resistance and It provides the effect of improving adhesion.

In addition, the thin film manufactured using the colored photosensitive resin composition includes a colorant having a specific color material combination, thereby providing an effect of preventing deterioration of color characteristics of an element including the thin film.

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

1 is a view showing a criterion for evaluating adhesion in the present invention.
2 is a graph measuring the spectral transmittance of a thin film prepared from the colored photosensitive resin composition according to the present invention.
3 is an enlarged graph of a portion having a wavelength range of 580 nm or less in FIG. 2 .
FIG. 4 is an enlarged graph of a portion having a wavelength range of 580 nm to 630 nm in FIG. 2 .
5 is an enlarged graph of a portion having a wavelength range of 630 nm to 780 nm in FIG. 2 .

The present invention includes (A) a colorant, (B) an alkali-soluble resin, (C) a thermosetting resin represented by the following formula (1), (D) a photopolymerizable compound, (E) a photopolymerization initiator, and (F) a solvent, (A) the colorant includes Pigment Red 179, Pigment Red 208, and carbon black, and the (E) photopolymerization initiator includes a compound represented by the following Chemical Formula 2, and a colored photosensitive resin composition using the same Provided are a manufactured color filter, and a display device including the color filter:

[Formula 1]

In Formula 1, n is an integer of 0 to 10.

[Formula 2]

In Formula 2,

A is CH or nitrogen,

R ₁ to R ₈ are each independently hydrogen, an alkyl group, Formula 3 below, -COR ₁₆ or -NO ₂ , R ₁₆ is an aryl group,

R ₁₃ is an alkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkyl group, or an aryl group.

[Formula 3]

In Formula 3,

Wherein R ₁₄ is hydrogen, a cycloalkyl group, an alkenyl group, an alkoxy group, an alkyl group or an aryl group, wherein R ₁₅ is an aryl group, a heteroaryl group, or an alkyl group, wherein X is -CO- or a direct connection, and * is is a bonding hand.

The colored photosensitive resin composition according to the present invention includes (C) a thermosetting resin represented by Formula 1 and (E) a photopolymerization initiator represented by Formula 2 having a low molecular weight, and is cured at a low temperature of 150° C. or less Even in this case, it can have high reliability.

The thin film manufactured using the colored photosensitive resin composition according to the present invention includes a colorant having a specific color material combination, thereby providing an effect of preventing deterioration of color characteristics of an element including the thin film.

Hereinafter, each component which comprises the coloring photosensitive resin composition of this invention is demonstrated in detail. However, the present invention is not limited by these components.

(A) Colorant

The colorant may include Pigment Red 179, Pigment Red 208, and carbon black, and may further include at least one pigment (a1), at least one dye (a3), or a mixture thereof.

As the colorant includes Pigment Red 179, Pigment Red 208, and carbon black, the spectral transmittance of a thin film prepared using the colored photosensitive resin composition is 10% or less at 580 nm or less, and 70% or less at 580 nm to 630 nm and may be 60% to 90% at 630 nm to 780 nm.

(a1) pigment

As the pigment, organic or inorganic pigments generally used in the art may be used, and these may be used alone or in combination of two or more. In addition, the pigment may be subjected to resin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, graft treatment of the pigment surface with a high molecular compound, etc., atomization treatment by sulfuric acid atomization method, etc., as necessary to remove impurities A cleaning treatment with an organic solvent, water, or the like, or a treatment for removing ionic impurities by an ion exchange method or the like may be performed.

As the organic pigment, various pigments used in printing inks, inkjet inks, etc. may be used, and specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, Perylene pigment, perinone pigment, dioxazine pigment, anthraquinone pigment, dianthraquinonyl pigment, anthrapyrimidine pigment, ananthrone pigment, indanthrone pigment, pravanthrone pigment, pyranthrone pigment, diketopyrroropyrrole pigment and the like.

In addition, as the inorganic pigment, a metal compound such as a metal oxide or a metal complex salt can be used, and specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, organic and metal oxides or composite metal oxides, such as black pigments, titanium black, and pigments that are black by mixing red, green and blue.

In particular, the organic and inorganic pigments include compounds classified as pigments in the color index (published by The Society of Dyers and Colorists), and more specifically, the color index (CI) number of pigments, but are not necessarily 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, 179, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264;

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

C.I. Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 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;

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

The pigment is preferably C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, 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, C.I. Pigment Green 58 may be selected.

The pigment may be included in an amount of 5 to 60% by weight, preferably 10 to 45% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When the pigment is included within the above range, the color density of the pixel is sufficient even when the thin film is formed, and the omission property of the non-pixel portion does not decrease during development, so that no residue is generated.

As the pigment, it is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of the method for uniformly dispersing the particle size of the pigment include a method of dispersing and dispersing the pigment dispersant (a2). According to the method, a pigment dispersion in a state in which the pigment is uniformly dispersed in a solution can be obtained. have.

(a2) Pigment dispersant

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

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

Specific examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, sorbitan fatty acid ester, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. are mentioned.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines are mentioned. have.

In addition, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter, 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, other resin type pigment dispersants may be used in addition to the acrylate-based dispersant. As the pigment dispersant of the other resin type, a pigment dispersant of a known resin type, particularly polyurethane, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids (partially) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl-containing polycarboxylic acids and modified products thereof, or free ) oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a carboxyl group with poly(lower alkyleneimine); 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 polyacrylates; adducts of ethylene oxide/propylene oxide; and phosphate esters.

As a commercial product of the above-mentioned other resin type pigment dispersant, as a cationic resin dispersant, for example, BYK (Big) Chemi Corporation's trade names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF's trade 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 from Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Trade names of Kawaken Fine Chemicals: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Trade names of Ajinomoto Corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Trade names of Kyoeisha Chemical Corporation: FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, fluorene DOPA-44, etc. are mentioned.

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

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

(a3) dye

The dye may be used without limitation as long as it has solubility in organic solvents. Preferably, it is preferable to use a dye that has solubility in organic solvents and can secure reliability such as solubility in alkali developer, heat resistance, and solvent resistance.

As the dye, an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide compound of an acid dye, and derivatives thereof may be used. In addition, azo-based, xanthene-based, phthalocyanine Acid dyes and derivatives thereof may also be selected. Preferably, the dye is a compound classified as a dye in the color index (published by The Society of Dyers and Colorists) or a known dye described in the dyeing note (color dye).

As a specific example of the dye, C.I. As a solvent dye,

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

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

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

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

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

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

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

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 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, etc. ;

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 , 382, 383, 394, 401, 412, 417, 418, 422, 426 and other red dyes;

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

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

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

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

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

Also 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 , 136, 138, 141 and other yellow dyes;

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 and other red dyes;

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, 293 blue dye;

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

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

Also, C.I. As a modanto dye,

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

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

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

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

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

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

Each of the above dyes may be used alone or in combination of two or more.

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

The content of the colorant may be 5 to 60% by weight, preferably 10 to 45% by weight based on the total weight of the solid content in the colored photosensitive resin composition. When the colorant is included within the above range, it is preferable that the color concentration of the pixel is sufficient when forming the thin film, and the omission property of the non-pixel portion is not reduced during development, so that residues are unlikely to be generated.

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

(B) alkali-soluble resin

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

The content of the alkali-soluble resin may be included in an amount of 10 to 80% by weight, preferably 10 to 70% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When the alkali-soluble resin is included within the above range, it is preferable because the solubility in the developer is sufficient to facilitate pattern formation, and the film reduction of the pixel portion of the exposed portion is prevented during development, and the omission of the non-pixel portion is improved. do.

It is preferable that the alkali-soluble resin has an acid value of 30 mgKOH/g to 150 mgKOH/g, and thus compatibility with the dye and stability over time of the colored photosensitive resin composition may be improved. When the acid value of the alkali-soluble resin is less than 30 mgKOH/g, it is difficult for the colored photosensitive resin composition to secure a sufficient development speed. And, compatibility with the dye may occur, and the dye may be precipitated in the colored photosensitive resin composition, or the stability of the colored photosensitive resin composition may be lowered with time to increase the viscosity.

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

The sum of the hydroxyl values of the alkali-soluble resin and the photopolymerizable compound is preferably 50 mgKOH/g to 250 mgKOH/g. When the sum of the hydroxyl groups of the alkali-soluble resin and the photopolymerizable compound is less than 50 mgKOH/g, a sufficient development rate cannot be ensured, and when it exceeds 250 mgKOH/g, the dimensional stability of the pattern to be formed is lowered, The straightness tends to be poor, and compatibility with the dye is lowered, which may cause a problem of stability over time.

(b1) an ethylenically unsaturated monomer having a carboxyl group

Specific examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; Polymer mono(meth)acrylates having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate, etc. are mentioned, and acrylic acid and methacrylic acid are preferable.

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

(b2) an ethylenically unsaturated monomer having a hydroxyl group

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

(b3) a compound having a glycidyl group

Specific examples of the compound 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, Dil ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, aryl glycidyl ether, glycidyl methacrylate Cidyl ester, etc., butyl glycidyl ether, aryl glycidyl ether, and methacrylic acid glycidyl ester are preferable, and two or more types may be used in combination.

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

(b4) unsaturated monomers

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

Styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, 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, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm -N-substituted maleimide compounds, such as methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl (meth) acrylate, 2- alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate;

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

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

(C) thermosetting resin

The thermosetting resin is characterized in that it is a compound represented by the following formula (1).

[Formula 1]

In Formula 1, n is an integer of 0 to 10.

The heat-setting resin is a low molecular weight material, and even when the colored photosensitive resin composition is cured at a low temperature at 150° C. or less, it can be sufficiently cured to provide high reliability.

The content of the thermosetting resin may be included in an amount of 0.1 to 20.0 wt%, preferably 0.1 to 10.0 wt%, more preferably 0.1 to 5.0 wt%, based on the total weight of the solid content in the colored photosensitive resin composition. can be included as When the thermosetting resin is included within the above range, it is preferable that the developability of the epigenetic photosensitive resin composition in an aqueous alkali solution is improved.

(D) photopolymerizable compound

The said photopolymerizable compound is a compound which can superpose|polymerize by the action|action of the photoinitiator mentioned later, and a monofunctional monomer, a bifunctional monomer, other polyfunctional monomer, etc. are mentioned.

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl p Rollidone etc. are mentioned. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. , bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like. Specific examples of other polyfunctional monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and di Pentaerythritol hexa(meth)acrylate etc. are mentioned. Among these, the polyfunctional monomer more than bifunctional is used preferably.

The photopolymerizable compound may be included in an amount of 5 to 50% by weight, preferably 7 to 45% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When the said photopolymerizable compound is contained within the said range, since there exists a tendency for the intensity|strength and smoothness of a pixel part to become favorable, it is preferable.

(E) photoinitiator

The photopolymerization initiator is characterized in that it comprises a compound represented by the following formula (2).

[Formula 2]

In Formula 2, A is CH or nitrogen, and R ₁ to R ₈ may each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, Formula 3 below, -COR ₁₆ or -NO ₂ .

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

[Formula 3]

In Formula 3, R ₁₄ is hydrogen, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a naphthyl group, and R ₁₅ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, wherein X is -CO- or a direct connection; , * may be a bond.

Alternatively, in Formula 2, A is CH or nitrogen, wherein R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ and R _{At least one pair of 8} may be represented by Formula 4 below.

[Formula 4]

Each of R ₉ to R ₁₂ may independently be hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, or a substituted or unsubstituted phenyl group.

Alternatively, in Formula 2, A is CH or nitrogen, and R ₁₃ is a substituted or unsubstituted C1-C20 alkyl group, C2-C12 alkenyl group, C4-8 cycloalkenyl group, C2-C20 It may be an alkynyl group having 12, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, or a naphthyl group.

The photopolymerization initiator may include, in addition to the compound represented by Formula 2, a photopolymerization initiator generally used in this field in an amount of 5 to 40 wt% based on the total weight of the photopolymerization initiator. The generally used photoinitiator includes, for example, a triazine-based compound, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, and an oxime-based compound.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, and 2-(3',4'-dime oxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxy naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2 -(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl-4,6-bis(trichloromethyl)-s-triazine, 2- Piphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichlorobetyl)-6-styryl-s-triazine, 2-(naphtho 1-yl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-trichloromethyl ( piperonyl)-6-triazine, 2,4-trichloromethyl(4'-methoxy styryl)-6-triazine, and the like.

Specific examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone , pt-Butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane -1-one and the like.

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoate, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethyl amino)benzophenone, 4,4'- bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc. are mentioned.

As the thioxanthone-based compound, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thi Oxanthone, 2-chlorothioxanthone, etc. are mentioned.

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

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

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

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

(F) solvent

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

The solvent is specifically ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, methyl ethyl ketone , acetone, methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, 3-ethyl ethoxypropionate, 3- Esters, such as methyl methoxypropionate, and cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned.

The solvent is preferably an organic solvent having a boiling point of 100 to 200 in terms of coatability and dryness, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalactate, 3-ethoxy ethyl propionate, 3-methoxy methyl propionate, etc. can be used.

Each of the solvents exemplified above may be used alone or in mixture of two or more, and may be included in 60 to 90 wt%, preferably 70 to 85 wt%, based on the total weight of the colored photosensitive resin composition of the present invention. When the solvent is contained within the above content range, the effect of improving the applicability when applied with an application device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), an inkjet, etc. It is preferable to provide

(G) additives

The colored photosensitive resin composition according to the present invention may further include additives as necessary, and in specific examples, at least one selected from a dispersant, a wetting agent, a silane coupling agent, and an anti-aggregation agent may be used.

A commercially available surfactant may be used as the dispersant, and the surfactant may include a silicone-based surfactant, a fluorine-based surfactant, a silicone-based surfactant having a fluorine atom, and mixtures thereof. Examples of the silicone-based surfactant include a surfactant having a siloxane bond. Commercially available products include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone 29SHPA, Toray Silicone SH30PA, polyether-modified silicone oil SH8400 (manufactured by Toray Silicone Co., Ltd.), KP321 , KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Silicon), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicon), etc. can be heard

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specifically, ProLinate (trade name) FC430, ProLinate FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapack (brand name) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, Megapack F183, Megapack R30 (manufactured by Dainippon Ink Chemical Co., Ltd.), ftop (brand name) EF301, ftop EF303, ftop EF351, ftop EF352 (manufactured by Shin-Akitakasei Co., Ltd.), Seo Pron (brand name) S381, Suflon S382, Suflon SC101, Suflon SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemicals, Inc.), BM-1000, BM-1100 (product) Name: manufactured by BMChemie) and the like.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specifically, megapack (brand name) R08, megapack BL20, megapack F475, megapack F477, megapack F443 (manufactured by Dainippon Ink Chemicals Co., Ltd.) and the like can be exemplified.

The wetting agent may include, for example, glycerin, diethylene glycol and ethylene glycol, and may include one or more selected from among them.

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

Examples of the aggregation inhibitor include sodium polyacrylate.

Color filter and liquid crystal display

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

A display device capable of including such a color filter may include a liquid crystal display device, an OLED display, a flexible display device, and the like, but is not limited thereto, and all display devices known in the art that can be applied may be exemplified.

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

First, after apply|coating a coloring photosensitive resin composition to a base material, volatile components, such as a solvent, are removed by heat-drying, and a smooth coating film is obtained.

As a coating method, it can carry out by the spin coating method, the casting|flow_spread coating method, the roll coating method, the slit-and-spin coating method, or the slit coating method, etc., for example. After application, heat drying (pre-baking) or drying under reduced pressure is performed to volatilize volatile components such as solvents. Here, the heating temperature is usually 70 to 200, preferably 80 to 130. The thickness of the coating film after heat drying is usually about 1 to 8 µm. In this way, the obtained coating film is irradiated with an ultraviolet-ray through the mask for forming the target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel rays are uniformly irradiated to the entire exposed portion and the mask and the substrate are precisely aligned. When irradiated with ultraviolet rays, the portion irradiated with ultraviolet rays is cured.

As the ultraviolet rays, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), etc. may be used. The irradiation amount of ultraviolet rays may be appropriately selected according to need, and the present invention is not limited thereto. When the cured coating film is brought into contact with a developer to dissolve the unexposed portion and developed, a desired pattern shape can be formed.

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

These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10 mass%, more preferably 0.03 to 5 mass%.

The surfactant in the alkaline developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, sorbitan fatty acid ester, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. are mentioned.

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

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts. These surfactants can be used individually or in combination of 2 or more types, respectively.

The concentration of the surfactant in the developer is usually 0.01 to 10 mass%, preferably 0.05 to 8 mass%, and more preferably 0.1 to 5 mass%. After image development, it washes with water and can also perform post-baking for 10 to 60 minutes at 150-230 as needed.

Hereinafter, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are merely illustrative, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, it embraces all modifications within the meaning and scope equivalent to those recorded in the claims. In addition, in the following examples and comparative examples, "%" and "part" indicating content are based on mass unless otherwise specified.

Preparation of colored photosensitive resin compositions according to Examples 1 to 4 and Comparative Examples 1 to 6

Example 1:

(A) C.I. Pigment Red 179 (pigment) 10 parts, C.I. Pigment Red 208 (pigment) 10 parts, carbon black 5 parts, BYK-2001 5.0 parts as a pigment dispersant and 70 parts propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill, (B) 28 parts of SPCY-6L (Showa Polymer) as alkali-soluble resin, (C) Thermosetting resin, 10 parts of Celloxide 2021P (Daisel Chemical) represented by the following formula 1-1, (D) A9550 as a photopolymerizable compound 6.5 parts, (E) 3 parts of OXE-02 (BASF) as a photopolymerization initiator, and 57 parts of propylene glycol monomethyl ether acetate as (F) solvent were mixed to prepare a colored photosensitive resin composition according to Example 1.

[Formula 1-1]

In Formula 1, n is 0.

Example 2:

(C) The thermosetting resin in the colored photosensitive resin composition according to Example 1 was replaced with Celloxide 2081 (Daisel Chemical) represented by the following Chemical Formula 1-2, to prepare a colored photosensitive resin composition according to Example 2.

[Formula 1-2]

In Formula 1, n is 1.

Example 3:

In the colored photosensitive resin composition according to Example 1, (E) the photopolymerization initiator was replaced with OXE-03 (BASF) to prepare a colored photosensitive resin composition according to Example 3.

Example 4:

In the colored photosensitive resin composition according to Example 1, (E) the photopolymerization initiator was replaced with SPI-03 (Samyang Corporation) to prepare a colored photosensitive resin composition according to Example 4.

Comparative Example 1:

In the colored photosensitive resin composition according to Example 1 (A) among the colorants, C.I. Pigment Red 179 was added to C.I. By replacing it with Pigment Red 177, a colored photosensitive resin composition according to Comparative Example 1 was prepared.

Comparative Example 2:

In the colored photosensitive resin composition according to Example 1 (A) among the colorants, C.I. Pigment Red 208 was added to C.I. By replacing it with Pigment Red 254, a colored photosensitive resin composition according to Comparative Example 2 was prepared.

Comparative Example 3:

(C) The thermosetting resin was removed from the colored photosensitive resin composition according to Example 1 to prepare a colored photosensitive resin composition according to Comparative Example 3.

Comparative Example 4:

(C) The thermosetting resin was removed from the colored photosensitive resin composition according to Example 4 to prepare a colored photosensitive resin composition according to Comparative Example 4.

Comparative Example 5:

In the colored photosensitive resin composition according to Example 4, (E) the photopolymerization initiator was replaced with I-369 (BASF) to prepare a colored photosensitive resin composition according to Comparative Example 5.

Comparative Example 6:

In the colored photosensitive resin composition according to Example 1, (C) the thermosetting resin was replaced with CNE-195XL-16 (Changchun Plastics) to prepare a colored photosensitive resin composition according to Comparative Example 6.

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

The colored photosensitive resin compositions according to Examples 1 to 4 and Comparative Examples 1 to 6 were coated on a bare glass substrate by spin coating, then placed on a heating plate and maintained at a temperature of 100 for 2 minutes to form a thin film. Then, a test photomask having a pattern for changing the transmittance in a range of 1 to 100% and a line/space pattern of 1 μm to 100 μm is placed on the thin film, and the distance from the test photomask is 200 μm was investigated. ^{At this time, the ultraviolet light source was irradiated with an illuminance of 50 mJ/cm 2} using a 1 KW high-pressure mercury lamp containing all of the g, h, and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet light was developed by immersing it in a developing solution of an aqueous KOH solution having a pH of 10.5 for 2 minutes. Post-process Bake was performed on 100 hotplates for 50 minutes. The film thickness of the color filters according to Examples 1 to 4 and Comparative Examples 1 to 6 using the colored photosensitive resin compositions according to Examples 1 to 4 and Comparative Examples 1 to 6 thus prepared was 3.5 μm.

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

1-1. Solvent resistance evaluation

The color filters according to Examples 1 to 4 and Comparative Examples 1 to 6 were immersed in PGMEA solvent, 60 for 10 minutes, and color change before and after evaluation was compared and evaluated. At this time, the color change is calculated by the following [Equation 1], and the value calculated by the following [Equation 1] is shown in [Table 1].

[Equation 1]

△Eab* =[(L*) ² +(a*) ² +(b*) ² ] ^1/2

[Equation 1] represents the color change in a three-dimensional colorimeter defined by L*, a*, b*, and the smaller the color change value calculated by [Equation 1], the more reliable the color filter manufacturing is It is possible.

<Evaluation criteria>

○: Excellent chemical resistance (there is no change in pattern, (Eab*) is less than 3.0)

△: good chemical resistance (there is a slight change in the pattern, or (Eab*) is 3.0 or more and less than 5.0)

×: poor chemical resistance (there is a change in the pattern, or (Eab*) is 5.0 or more)

1-2. Adhesion evaluation

After immersing the color filters according to Examples 1 to 4 and Comparative Examples 1 to 6 in PGMEA at room temperature and waiting for 10 minutes, OK and NG were judged by whether the formed pattern was detached. 1 is a view showing a criterion for evaluating such adhesion. If the pattern remains after immersion, it is judged as OK, if the pattern is detached after immersion, it is judged as NG, and it is shown in [Table 1] below.

division solvent resistance adhesion Example 1 O OK Example 2 O OK Example 3 O OK Example 4 O OK Comparative Example 1 O OK Comparative Example 2 O OK Comparative Example 3 X NG Comparative Example 4 X NG Comparative Example 5 X NG Comparative Example 6 X NG

Referring to [Table 1], the color filters according to Comparative Examples 2 to 6 were excellent in solvent resistance and adhesion of the color filters according to Examples 1 to 4, which were prepared using the colored photosensitive resin composition according to the present invention. It can be seen that the solvent resistance and adhesion are not good.

1-3. Spectral transmittance measurement

Spectral transmittance of the color filters according to Example 1 and Comparative Examples 1 and 2 was measured using a microscopic spectrophotometer, OSP-SP2000 (Olympus), and are shown in FIGS. 2 to 5 .

Since the color filters according to Examples 1 to 4 and Comparative Examples 3 to 6 contain the same colorant and exhibit substantially the same spectral transmittance, only the spectral transmittances of Example 1 and Comparative Examples 1 and 2 are shown in FIGS. did

2 to 5, the spectral transmittance of the color filter according to Example 1, prepared using the colored photosensitive resin composition according to the present invention, is 10% or less at 580 nm or less, 70% or less at 580 nm to 630 nm, and 630 nm to While it is included in the range of 60% to 90% at 780nm, it can be seen that the spectral transmittances of Comparative Examples 1 and 2 are not.

Therefore, in the case of manufacturing a color filter using the colored photosensitive resin composition according to the present invention, the degree of curing, which is an important characteristic of a low-temperature cured product, is improved, and solvent resistance and adhesion are improved to improve the reliability of the color filter, and at the same time, the reliability of the color filter. It can be seen that the spectral transmittance is included in the range of 10% or less at 580 nm or less, 70% or less at 580 nm to 630 nm, and 60% to 90% at 630 nm to 780 nm, indicating excellent spectral transmittance.

Claims (9)

(A) a colorant, (B) an alkali-soluble resin, (C) a thermosetting resin represented by the formula (1), (D) a photopolymerizable compound, (E) a photopolymerization initiator and (F) a colored photosensitive resin composition comprising a solvent ,
The (A) colorant includes Pigment Red 179, Pigment Red 208 and carbon black,
The (E) photopolymerization initiator is a compound represented by the following formula (2), and includes at least one of OXE-03 (BASF) and SPI-03 (Samyang),
The thin film prepared from the colored photosensitive resin composition,
Spectral transmittance is 10% or less at 580 nm or less,
Spectral transmittance is 70% or less at 580 nm to 630 nm,
Colored photosensitive resin composition, characterized in that the spectral transmittance is 60% to 90% at 630 nm to 780 nm:
[Formula 1]

In Formula 1, n is an integer of 0 to 10.
[Formula 2]

In Formula 2,
A is CH or nitrogen,
R ₁ to R ₈ are each independently hydrogen, an alkyl group, Formula 3 below, -COR ₁₆ or -NO ₂ , R ₁₆ is an aryl group,
R ₁₃ is an alkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkyl group, or an aryl group.
[Formula 3]

In Formula 3,
Wherein R ₁₄ is hydrogen, a cycloalkyl group, an alkenyl group, an alkoxy group, an alkyl group or an aryl group, wherein R ₁₅ is an aryl group, a heteroaryl group, or an alkyl group, wherein X is -CO- or a direct connection, and * is is a bonding hand.
The method according to claim 1,
The colored photosensitive resin composition is a colored photosensitive resin composition, characterized in that the low-temperature curing at 150 ℃ or less.
delete delete delete The method according to claim 1,
With respect to the total weight of the solid content in the colored photosensitive resin composition,
The (A) colorant is included in an amount of 0.5 to 80% by weight,
The (B) alkali-soluble resin is included in an amount of 10 to 80% by weight,
The (C) thermosetting resin represented by Formula 1 is included in an amount of 0.1 to 20.0% by weight,
The (D) photopolymerizable compound is included in 5 to 50% by weight,
The (E) photopolymerization initiator is included in an amount of 0.1 to 10% by weight,
The (F) solvent is a colored photosensitive resin composition, characterized in that it is included in an amount of 60 to 90% by weight based on the total weight of the colored photosensitive resin composition.
delete A color filter comprising a colored pattern made of the colored photosensitive resin composition of any one of claims 1, 2 and 6.
A display device comprising the color filter of claim 8 .

Images