KR20200064829A - A colored photo sensitive resin composition, a color filter comprising the same, and a display devide comprising the color filter - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition comprising: a colored dispersion including a coloring agent and a benzophenone compound represented by chemical formula 1; an alkali-soluble resin; a photopolymerizable compound; a photopolymerization initiator; and a solvent, wherein the photopolymerization initiator includes at least one selected from a carbazole-based initiator and a fluorene oxime-based initiator, to a color filter produced using the same, and to a display device comprising the same. The colored photosensitive resin composition has improved solvent resistance and adhesion.

Description

A colored photosensitive resin composition, a color filter manufactured using the same, and a display device including the color filter {A COLORED PHOTO SENSITIVE RESIN COMPOSITION, A COLOR FILTER COMPRISING THE SAME, AND A DISPLAY DEVIDE COMPRISING 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.

The 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 image pickup device, the liquid crystal display device, etc. is composed of three colored patterns of red, green, and blue, or yellow, magenta, and cyan ( Cyan) consists of three colored coloring patterns.

The coloring pattern of each of the color filters is generally formed using a coloring photosensitive resin composition containing a coloring agent 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 coloring photosensitive resin composition is usually performed by a lithography process.

The coloring pattern of each of the color filters is generally formed using a coloring photosensitive resin composition containing a coloring agent 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 coloring photosensitive resin composition is usually performed by a lithography process.

The coloring photosensitive resin is an essential material such as a color filter, a liquid crystal display material, an organic light emitting element, and a display. For example, in a color filter of a color liquid crystal display, a light blocking layer using a black photosensitive composition is formed at a boundary between the coloring layers to enhance the contrast and color development effect of red, green, and blue. In addition, recently, it is required to be positioned on an array substrate to form a spacer for maintaining a cell gap, as well as a role of a black matrix, so that various roles can be performed at once. Accordingly, not only an optical effect for basic shading, but also a property having good elastic modulus and reliability is required.

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

Republic of Korea Registered Patent No. 10-1648607

The present invention is to improve the above-mentioned conventional technical problems, and by including a carbazole-based and/or fluorene oxime-based photopolymerization initiator, it has excellent curing degree even at low temperatures, and has improved properties such as solvent resistance and adhesion. It is an object to provide a photosensitive resin composition.

In addition, the present invention is to include a benzophenone-based compound in the colored dispersion, the blue spectrum has a transmittance of 435nm to 455nm with a maximum transmittance of 76% or more, and an object of the present invention is to provide a color filter capable of achieving a half width of 93nm or less.

In addition, an object of the present invention is to prevent deterioration in color characteristics of a device including a thin film prepared by using the colored photosensitive resin composition.

In addition, an 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 order to achieve the above object, the present invention, a colorant, and a colored dispersion comprising a benzophenone compound of Formula 1; Alkali-soluble resin; Photopolymerizable compounds; Photopolymerization initiator; And a colored photosensitive resin composition comprising a solvent, wherein the colorant includes at least one selected from blue pigments and purple pigments,

The photopolymerization initiator provides a colored photosensitive resin composition comprising one or more selected from carbazole-based and fluorene oxime-based.

[Formula 1]

In addition, the present invention provides a color filter made of 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 one or more photopolymerization initiators selected from carbazole-based and fluorene oxime-based polymers, so that even when cured at a low temperature, the curability is excellent, improving the solvent resistance and adhesion of the colored photosensitive resin composition Provides

In addition, the thin film prepared by using the colored photosensitive resin composition includes a benzophenone compound represented by Chemical Formula 1 in a colored dispersion, and has a blue spectral transmittance of 435 nm to 455 nm, a maximum transmittance of 76% or more, and a half width of 93 nm or less By doing so, it provides an effect of preventing degradation of color characteristics of a device including a pattern made of the colored photosensitive resin composition.

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

1 is a view of the adhesion evaluation criteria.
Figure 2 is a graph measuring the spectral transmittance up to about 380 to 780.0 nm in the wavelength range of the color filters prepared with the compositions of Examples 1, 4 and 5 and Comparative Examples 1, 4 and 5.
Figure 3 is a graph measuring the spectral transmittance up to about 380 to 580.0 nm in the wavelength range of the color filters prepared with the compositions of Examples 1, 4 and 5 and Comparative Examples 1, 4 and 5.
4 is a graph showing each half-width range of Examples 1, 4 and 5 and Comparative Examples 1, 4 and 5 in the wavelength range of about 380 to 580.0 nm.

The present invention, a colorant and a colored dispersion comprising a benzophenone compound of formula 1; Alkali-soluble resin; A photosensitive resin composition comprising a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant includes at least one selected from blue pigments and purple pigments, and the photopolymerization initiator is selected from carbazole and fluorene oxime systems 1 It provides a colored photosensitive resin composition, a color filter manufactured using the same, and a display device comprising the color filter.

[Formula 1]

Colored photosensitive resin composition

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

(A) A colored dispersion containing a colorant

The colored dispersion liquid comprises at least one selected from a blue pigment and a purple pigment as a colorant, and is characterized by including a benzophenone-based compound of Formula 1.

coloring agent

Blue pigment and/or purple pigment

In the present invention, the blue pigment is more specifically, C.I. Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 16, 21, 28, 60, 64 and 76, and may be one or more selected from the purple pigments. Pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38. In the present invention, the thin film prepared by using the coloring photosensitive resin composition containing pigment blue 15:6 as a blue pigment and pigment violet 23 as a purple pigment, and containing a benzophenone-based compound represented by Formula 1 The transmittance at a wavelength of 435 nm to 445 nm may be 76% or more, more preferably 76% or more and 100% or less, and a half width of 93 nm or less, more preferably 50 nm or more and 93 nm or less.

Benzophenone compounds

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

[Formula 1]

When the benzophenone compound is fired at a temperature of 170° C. or lower, the transmittance of the short wavelength region of the blue spectrum is lowered, and when used in combination with pigments such as Pigment Blue 15:6 and Pigment Violet 23, the half width of the blue spectrum is increased. There is an advantage that can be effectively reduced.

The content of the benzophenone compound may be included in an amount of 0.1 to 20.0% by weight, preferably 0.1 to 10.0% by weight, more preferably 0.1 to 5.0% by weight based on the total weight of solids in the colored photosensitive resin composition. It can be included as When the thermosetting resin is included within the above range, it is preferable to achieve effective half-width reduction of the photosensitive resin composition and improve developability for an aqueous alkali solution.

In addition to the blue pigment and the purple pigment, the colorant may additionally include one or more (a1) pigments as necessary, and may further include one or more (a3) dyes as necessary.

(a1) pigment

The colorant in the present invention may further include an organic pigment or an inorganic pigment generally used in the art, if necessary.

If necessary, the pigment may be subjected to resin treatment, surface treatment using an acidic or basic group-derived pigment derivative, graft treatment of a pigment surface with a polymer compound, atomization treatment using a sulfuric acid atomization method, or an organic solvent for removing impurities. In addition, washing treatment with water or the like, or removal of ionic impurities by ion exchange may also be performed.

As the organic pigment, various pigments used in printing ink, inkjet ink, and the like can be used, specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, Perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthantrone pigments, indanthrone pigments, pravanthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments And the like.

In addition, a metal compound such as a metal oxide or a metal complex salt may be used as the inorganic pigment. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, organic And oxides of metals such as black pigments, titanium blacks and reds, greens, and blues, and black pigments, or composite metal oxides.

In particular, examples of the organic pigments and inorganic pigments include compounds classified as pigments in the color index (published by The society of Dyers and Colourists), and more specifically, the following color index (CI) numbers. Pigments can be mentioned, but are not 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, 179, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264;

C.I. Pigment Green 7, 10, 15, 25, 36, 47, 58 and 59;

C.I pigment brown 28;

C.I pigment black 1 and 7;

The pigment, which may be additionally included, 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 179, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I., C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58 and C.I. Pigment Green 59.

In the present invention, the total content of the pigments included in the present invention, including the blue pigment and the purple pigment, which are essentially included, is 5 to 100% by weight, preferably 25 to 60% by weight, based on the total solid content of the colored dispersion. %. When the pigment is included in the above range, it is preferable to form a thin film, since the color density of the pixel is sufficient, and since the omission of the non-pixel portion does not decrease during development, residues are not generated.

It is preferable to use a pigment dispersion liquid in which the particle diameter of the pigment is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment may include a method of dispersing by containing a pigment dispersant (a2), and a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution according to the above method can be obtained. have.

(a2) pigment dispersant

The pigment dispersant is added to maintain the deagglomeration and stability of the pigment, and can be used without limitation, generally used in the art. Specific examples of the pigment dispersant are cationic, anionic, nonionic, and 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.

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

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

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, And polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Other examples include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and polyethyleneimines. have.

In addition, the pigment dispersant preferably contains an acrylate-based dispersant (hereinafter, an acrylate-based dispersant) including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). Commercial products of the acrylate-based dispersants include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150, and the acrylate-based dispersants can be used alone or in combination of two or more. Can be.

In addition to the acrylate-based dispersant, other resin-type pigment dispersants may be used. As the other resin type pigment dispersant, a known resin type pigment dispersant, in particular of polyurethane, polyacrylate, polycarboxylic acid ester, unsaturated polyamide, polycarboxylic acid, and polycarboxylic acid (partially) 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 ) Oily dispersants such as amides or salts thereof formed by the reaction of polyesters having carboxyl groups with poly(lower alkyleneimines); 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; Addition products of ethylene oxide/propylene oxide; And phosphate esters.

Commercially available products of the other resin type pigment dispersants include, for example, cationic resin dispersants, for example, BYK (Big) Chemicals: 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 Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 /10; Trade names of Kawaken Fine Chemicals: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Ajinomoto's trade names: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Trade names of Kyoeisha Chemicals: FLORENE DOPA-17HF, Floren DOPA-15BHF, Floren DOPA-33, Floren DOPA-44, and the like.

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

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

(a3) Dye

In the present invention, a dye as a colorant may be included in one or more kinds if necessary, and the dye can be used without limitation as long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye which has a solubility in an organic solvent and ensures solubility in an alkali developer and reliability such as heat resistance and solvent resistance.

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

Specific examples 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, and 62;

C.I. Blue dyes such as solvent blue 5, 35, 36, 37, 44, 59, 67, 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. C.I. excellent in solubility in organic solvents among solvent dyes. Solvent Yellow 14, 16, 21, 56, 151, 79, 93; preferred and C.I. Solvent Yellow 21, 79; are more preferred.

In addition, C.I. As an acid dye,

CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 Yellow dyes such as, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 ;

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 having excellent solubility in organic solvents in 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 , Yellow dyes such as 136, 138, 141;

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

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

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

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

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

In addition, 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, and 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 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;

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

When a dye is further included in the colorant, the content of the dye is included in 0.5 to 50% by weight based on the total weight of solids in the colored photosensitive resin composition, and 1 to 40% by weight may be preferable, and 1 to 20% by weight May be more desirable. When the dye is included within the content range, a problem of deterioration in reliability in which the dye is eluted by an organic solvent after pattern formation may be prevented, and sensitivity may be increased to have an effect.

The content of the colorant may be included in 5 to 60% by weight, preferably 10 to 45% by weight based on the total weight of solids in the colored photosensitive resin composition. When the colorant is included in the above range, it is preferable that the color density of the pixel is sufficient when forming a thin film, and the omission of the non-pixel portion does not deteriorate during development, so that residue is less likely to occur.

In the present invention, the total weight of solids 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 produced by copolymerizing an ethylenically unsaturated monomer (b1) having a carboxyl group as an essential component in order to have solubility with respect to an alkali developer used in the developing treatment process when forming a pattern.

(b1) ethylenically unsaturated monomer having a carboxyl group

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 these anhydrides of dicarboxylic acids; and mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate, and acrylic acid and methacrylic acid are preferred.

The alkali-soluble resin can be prepared by copolymerizing the ethylenically unsaturated monomer having a carboxyl group with an ethylenically unsaturated monomer having a hydroxyl group (b2). Alternatively, the alkali-soluble resin may be prepared by copolymerizing the copolymer of the ethylenically unsaturated monomer having a carboxyl group with a compound (b3) having a glycidyl group. Alternatively, the alkali-soluble resin may be prepared by copolymerizing the ethylenically unsaturated monomer having the carboxyl group, the ethylenically unsaturated monomer having the hydroxyl group, and the compound having the glycidyl group.

(b2) 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, and 2-hydroxy- 3-phenoxypropyl (meth)acrylate, N-hydroxyethyl acrylamide, and the like, and 2-hydroxyethyl (meth)acrylate are preferred, and two or more kinds can be used in combination.

(b3) Compound having glycidyl group

Specific butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, ethyl glycyl of the compound having the glycidyl group Diyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, aryl glycidyl ether, methacrylic acid glyc There is a cydyl ester, and butyl glycidyl ether, aryl glycidyl ether, and methacrylic acid glycidyl ester are preferred, and two or more kinds can be used in combination.

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

(b4) unsaturated monomer

The unsaturated monomers may be used alone or in combination of two or more, respectively, and are not limited to the following examples.

Styrene, vinyl toluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, 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, 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]decane-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.

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

The acid value of the alkali-soluble resin is preferably 30 mgKOH/g to 150 mgKOH/g, and accordingly, compatibility with the dye and light stability 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 developing speed, and when it exceeds 150 mgKOH/g, adhesion to the substrate is reduced, and a short circuit of the pattern is likely to occur. In addition, a compatibility problem with the dye occurs, and the dye in the colored photosensitive resin composition may precipitate or the viscosity of the colored photosensitive resin composition may deteriorate and the viscosity may increase.

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

The sum of the hydroxyl value of the alkali-soluble resin and the photopolymerizable compound described below is preferably 50 mgKOH/g to 250 mgKOH/g. When the sum of the alkali-soluble resin and the hydroxyl group of the photopolymerizable compound is less than 50 mg·KOH/g, a sufficient development rate cannot be secured, and when it exceeds 250 mg·KOH/g, the dimensional stability of the pattern formed It is easy to deteriorate, and the straightness of the pattern tends to be poor, and compatibility with the dye may be deteriorated, resulting in a problem of stability over time.

(C) Photopolymerizable compound

The photopolymerizable compound is a compound that can be polymerized by the action of the photopolymerization initiator described below, and examples thereof include a monofunctional monomer, a bifunctional monomer, and other polyfunctional monomers.

Specific examples of the monofunctional monomer include nonylphenylcarbitolacrylate, 2-hydroxy-3-phenoxypropylacrylate, 2-ethylhexylcarbitolacrylate, 2-hydroxyethylacrylate, and N-vinylpy And rollidone. As specific examples of the bifunctional monomer, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 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 And pentaerythritol hexa(meth)acrylate. Among them, a bifunctional or higher polyfunctional monomer is preferably used.

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

(D) Photopolymerization initiator

The photopolymerization initiator of the present invention may include one or more photopolymerization initiators selected from carbazole and fluorene oxime systems.

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

[Formula 2]

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

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

[Formula 3]

In Chemical 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, and X is -CO- or a direct linking day Can be.

Or, in Chemical Formula 2, A is -CH- or N, and R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ And R ₈ At least one pair may be the following formula (4).

[Formula 4]

R ₉ to R ₁₂ may be each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted phenyl group.

Alternatively, in Formula 2, A is carbon or nitrogen, and R ₁₃ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, or 2 to 2 carbon atoms. It may be an alkynyl group of 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 Chemical Formula 2, a photopolymerization initiator generally used in this field, in an amount of 5 to 40% by weight based on the total weight of the photopolymerization initiator. Examples of the photopolymerization initiator generally used include triazine-based compounds, acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, and oxime-based compounds.

The triazine-based compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloro methyl)-s-triazine, 2-(3',4'-dime Thoxy styryl)-4,6-bis(trichloro methyl)-s-triazine, 2-(4'-methoxy naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2 -(p-methoxy phenyl)-4,6-bis(trichloro methyl)-s-triazine, 2-(p-tolyl-4,6-bis(trichloromethyl)-s-triazine, 2- Piphenyl-4,6-bis(trichloro methyl)-s-triazine, bis(trichloro betyl)-6-styryl-s-triazine, 2-(naphtho 1-yl)-4,6- Bis(trichloro methyl)-s-triazine, 2-(4-methoxy naphtho 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-trichloro methyl ( Piperonyl)-6-triazine, 2,4-trichloro methyl (4'-methoxy styryl)-6-triazine, and the like.

Specific examples of the acetophenone-based compound, 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 And -1-one.

The benzophenone compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethyl amino)benzophenone, 4,4'- And bis(diethyl amino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

Examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4-diisopropyl thi. Oxanthone, 2-chloro thioxanthone, etc. are mentioned.

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

The oxime-based compound is 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione and 1-(o-acetyloxime)-1-[9-ethyl- And 6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone.

In addition to the exemplified above, carbazole-based compounds, diketone compounds, sulfonium borate-based compounds, diazo-based, biimidazole-based compounds, and the like can 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 solids in the colored photosensitive resin composition. When the photopolymerization initiator is included in the above range, photopolymerization occurs sufficiently during exposure in the pattern forming process, and may not cause a decrease in transmittance due to the unreacted initiator remaining after the photopolymerization.

(E) Solvent

If the solvent is effective for dissolving other components included in the colored photosensitive resin composition, a solvent used in a typical colored photosensitive resin composition can be used without particular limitation, and in particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters Classes or amides are preferred.

The solvent is specifically ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoalkyl ethers such as 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, 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, mesitylene, and methyl ethyl ketone , Ketones such as acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin, 3-ethoxypropionate ethyl, 3- And esters such as methyl methoxypropionate, and cyclic esters such as γ-butyrolactone.

The solvent is preferably an organic solvent having a boiling point of 100°C to 200°C in terms of coatability and dryness, and more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalac Tate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like can be used.

The solvents exemplified above may be used alone or in combination of two or more, and may be included in an amount of 60 to 90% by weight, preferably 70 to 85% by weight based on the total weight of the colored photosensitive resin composition of the present invention. When the solvent is included within the above content range, the effect of improving the coatability when applied with an application device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, etc. It is preferred because it provides.

(F) additive

The colored photosensitive resin composition according to the present invention may further include additives as necessary, and for example, at least one selected from dispersants, wetting agents, silane coupling agents, and anti-agglomeration agents may be used.

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

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Prolinate (brand 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 Kagaku Kogyo Co., Ltd.), F-top (brand name) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Seo Pron (brand name) S381, Surfon S382, Surfon SC101, Surfon SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemicals Gen.), BM-1000, BM-1100 (product Name: BMChemie).

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

Examples of the wetting agent include glycerin, diethylene glycol, and ethylene glycol, and may include one or more selected therefrom.

Examples of the silane coupling agent include aminopropyl triethoxysilane, γ-mercaptopropyl trimethoxysilane, and γ-methacryloxypropyl trimethoxysilane, and commercially available products include SH6062, SZ6030 (Toray-Dow Corning Silicon co., Ltd.), KBE903, KBM803 (Shin-Etsu silicone co., Ltd.).

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 that may include such a color filter may include a liquid crystal display device, an OLED, and a flexible display, but is not limited thereto, and all display devices known in this field that can be applied may be exemplified.

The color filter can be produced by applying the colored photosensitive resin composition of the present invention on the substrate, photocuring and developing to form a pattern.

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

As the coating method, for example, it can be carried out by a spin coating method, a flexible coating method, a roll coating method, a slit and spin coating or a slit coating method. After application, heating and drying (pre-baking) or drying under reduced pressure is followed by heating to volatilize volatile components such as solvents. Here, the heating temperature is usually 70 to 200°C, preferably 70 to 170°C, more preferably 80 to 130°C. The thickness of the coating film after heating and drying is usually about 1 to 8 µm. The coating film thus obtained is irradiated with ultraviolet light through a mask for forming a target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel light is uniformly irradiated to the entire exposed portion and accurate alignment of the mask and the substrate is performed. When irradiated with ultraviolet rays, curing of a region irradiated with ultraviolet rays is achieved.

As the ultraviolet rays, g-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm), or the like can be used. The irradiation amount of ultraviolet light may be appropriately selected as necessary, and the present invention is not limited thereto. The desired pattern shape can be formed by contacting the developer after curing is completed by dissolving and developing the non-exposed portion.

The developing method may be any of a liquid addition method, a dipping method, and a spray method. Further, the substrate may be tilted at an arbitrary angle during development. The supernatant is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be any of inorganic and organic alkaline compounds. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, dihydrogen 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, And monoisopropylamine, diisopropylamine, and ethanolamine.

These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The concentration of the alkaline compound in the alkali developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The surfactant in the alkali developer may use at least one selected from the group consisting of nonionic surfactants, anionic surfactants, or cationic surfactants.

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, And polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alcohol amines.

Specific examples of the anionic surfactant include lauryl alcohol sulfate, higher alcohol sulfate ester salts such as sodium sterol or oleyl alcohol sulfate ester, alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate, and dodecylbenzenesulfonic acid And alkylarylsulfonates such as sodium and sodium dodecylnaphthalenesulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride or quaternary ammonium salts. These surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass. After development, it is washed with water, and if necessary, post-baking may be performed at 90 to 170°C, preferably 90 to 150°C for 10 to 60 minutes. The criterion for low temperature curing may mean that the temperature in the post-baking process is low temperature.

Hereinafter, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the invention is indicated in the claims, and furthermore, includes all changes within the meaning and scope equivalent to the claims of the claims. In addition, "%" and "part" showing content in the following Examples and Comparative Examples are based on mass unless otherwise specified.

Preparation of colored photosensitive resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 5

Example 1:

(A) C.I. Pigment Blue 15:6 (pigment) 10 parts, C.I. Pigment Violet 23 (pigment) 5 parts, (C) 5 parts of a benzophenone compound represented by the following Chemical Formula 1, 4.0 parts of BYK-2001 as a pigment dispersant and 76 parts of propylene glycol monomethyl ether acetate were mixed, and a bead mill was used. After sufficiently dispersing the pigment, 31 parts of the pigment dispersion (B) 10 parts of SPCY-6L (Showa Polymer Co.) as an alkali-soluble resin, (D) 5 parts of A9550 as a photopolymerizable compound, (E) OXE as a photopolymerization initiator A colored photosensitive resin composition according to Example 1 was prepared by mixing 50 parts of propylene glycol monomethyl ether acetate with -02 (BASF) 4 parts and (F) solvent.

[Formula 1]

Prepared in the same manner as in Example 1, (C) benzophenone compound and (E) to confirm the effect of the photopolymerization initiator by applying a change of the components, Examples 2 to 5, Comparative Examples as shown in Table 1. The composition was composed from 1 to 5.

[Table 1]

(Unit: part)

*week

[Formula 2]

[Formula 3]

OXE-03 (BASF)

SPI-03 (Samyang Corporation)

I-369(Irgacure-369;ciba)

I-907(Irgacure-907;ciba)

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

The colored photosensitive resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 5 were coated on a bare glass substrate by spin coating, then placed on a heating plate and held at a temperature of 100° C. for 2 minutes to form a thin film. Subsequently, a test photomask having a pattern for changing the transmittance stepwise in the range of 1 to 100% and a line/space pattern of 1 μm to 100 μm was placed on the thin film, and the distance from the test photomask was 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 g, h, and i rays, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes to develop. After the process, the baking was performed for 60 minutes on a 130°C hotplate. The film thickness of each color filter formed by using the colored photosensitive resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 5, thus prepared, was 2.6 μm.

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

1-1. Evaluation of solvent resistance

The color filters according to Examples 1 to 5 and Comparative Examples 1 to 5 were immersed in a PGMEA solvent at 60°C for 10 minutes to compare and evaluate color changes before and after the evaluation. At this time, the color change is calculated by [Equation 1] below, and the values calculated by [Equation 1] below are shown in [Table 2].

[Equation 1]

△Eab* =[(△L*) ² +(△a*) ² +(△b*) ² ] ^1/2

[Equation 1] represents the color change in the 3D colorimeter defined by L*, a*, b*, and the smaller the color change value calculated by [Equation 1], the higher the reliability of the color filter production. It is possible.

<Evaluation criteria>

○: Excellent (the pattern does not change, △(Eab*) is less than 3.0)

△: Good (the pattern is slightly changed, △ (Eab*) is 3.0 or more and less than 5.0)

×: Bad (pattern change or △(Eab*) is 5.0 or more)

The evaluation results are shown in [Table 2].

1-2. Adhesion evaluation

The color filters according to Examples 1 to 5 and Comparative Examples 1 to 5 were immersed in PGMEA at room temperature, waited for 10 minutes, and then OK and NG were determined through whether or not the formed pattern was detached. 1 is a view showing a criterion for evaluating such adhesion. If the pattern remains after immersion, it is OK, and if the pattern is detached after immersion, it is judged as NG, and is shown in Table 2 below.

1-3. Spectral transmittance measurement

The color filters according to Examples 1, 4, 5 and Comparative Examples 1 4 and 5 were measured in spectral transmittance with a microscopic spectrophotometer OSP-SP2000 (Olympus Co.), and are shown in FIGS. 2 to 4, respectively. According to the half width and the maximum transmittance are shown in [Table 2].

Since the color filters according to Examples 2 to 3 and Comparative Examples 2 and 3 include the same colorant and exhibit substantially the same spectral transmittance, FIG. 1 shows Examples 1, 4, 5 and Comparative Examples 1, 4 and 5 Only spectral transmittance is shown.

2 and [Table 2], the highest spectral transmittance of the color filters according to Examples 1, 4, and 5 prepared using the colored photosensitive resin composition according to the present invention is 76% or more, and the half-value width is 93 nm or less. Can be seen.

※Definition of half width:

A% = highest transmittance Ⅹ 1/2

B nm = short wavelength side x-axis wavelength corresponding to A% transmittance

C nm = long wavelength side x-axis wavelength corresponding to A% transmittance

Half width (nm) = C-B

[Table 2]

Accordingly, when a color filter is manufactured using the colored photosensitive resin composition according to the present invention, the curing degree, which is an important characteristic of a low-temperature curing product, is improved to improve solvent resistance and adhesion, thereby improving the reliability of the color filter, and A characteristic blue spectrum with a maximum transmittance of 76% or more and a half width of 93 nm or less at a wavelength of 435 nm to 445 nm can be achieved.

Claims (10)

A coloring agent, and a coloring dispersion comprising a benzophenone compound represented by Formula 1; Alkali-soluble resin; Photopolymerizable compounds; Photopolymerization initiator; And a colored photosensitive resin composition comprising a solvent,
The colorant includes at least one selected from blue pigments and purple pigments,
The photopolymerization initiator is a colored photosensitive resin composition comprising at least one selected from carbazole-based and fluorene oxime-based:
[Formula 1]

. The method according to claim 1,
The blue pigment is at least one selected from the group consisting of CI Pigment Blue 15:3, 15:4, 15:6, 21, 28, 60, 64 and 76,
The purple pigment is one or more selected from CI pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38, colored photosensitive resin composition. The method according to claim 1,
The photopolymerization initiator is to include a structure represented by the formula (2),
Colored photosensitive resin composition:
[Formula 2]

In Chemical Formula 2, A is -CH- or nitrogen, and R ₁ to R ₈ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, Chemical Formula 3, -COR ₁₆ or -NO ₂ ,
The R ₁₆ may be an aryl group having 6 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms.
[Formula 3]

In Chemical 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, and X is -CO- or a direct linking day Can be. The method according to claim 3,
In Formula 2, at least one pair of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ and R ₈ is Colored photosensitive resin composition characterized in that:
[Formula 4]

In Chemical Formula 4,
R ₉ to R ₁₂ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted phenyl group. The method according to claim 3,
In Formula 2, R ₁₃ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, or 3 to 10 carbon atoms. Is a cycloalkyl group, a phenyl group, or a naphthyl group;
The R ₁₆ is a colored photosensitive resin composition, characterized in that an aryl group having 6 to 20 carbon atoms substituted or unsubstituted with at least one substituent 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. The method according to claim 1,
The thin film made of the coloring photosensitive resin composition,
Colored photosensitive resin composition, characterized in that the transmittance at a wavelength of 435nm to 445nm is 76% or more. The method according to claim 1,
The thin film made of the coloring photosensitive resin composition,
A colored photosensitive resin composition having a half width of 93 nm or less. The method according to claim 1,
With respect to the total weight of solids in the coloring photosensitive resin composition,
5 to 60% by weight of the colorant,
0.1 to 20.0% by weight of the benzophenone compound,
10 to 80% by weight of the alkali-soluble resin,
5 to 50% by weight of the photopolymerizable compound
0.1 to 10% by weight of the photopolymerization initiator,
The solvent is a colored photosensitive resin composition, characterized in that contained in 60 to 90% by weight relative to the total weight of the colored photosensitive resin composition. A color filter comprising a colored pattern made of the colored photosensitive resin composition of claim 1. A display device comprising the color filter of claim 9.

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