KR20150107156A - Colored Photosensitive Resin Composition and Color Filter Comprising the Same - Google Patents
Colored Photosensitive Resin Composition and Color Filter Comprising the Same Download PDFInfo
- Publication number
- KR20150107156A KR20150107156A KR1020140029648A KR20140029648A KR20150107156A KR 20150107156 A KR20150107156 A KR 20150107156A KR 1020140029648 A KR1020140029648 A KR 1020140029648A KR 20140029648 A KR20140029648 A KR 20140029648A KR 20150107156 A KR20150107156 A KR 20150107156A
- Authority
- KR
- South Korea
- Prior art keywords
- resin composition
- photosensitive resin
- colored photosensitive
- acid
- dye
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
- G03F7/0295—Photolytic halogen compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
Abstract
Description
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition and a color filter manufactured using the same, and more particularly, to a colored photosensitive resin composition capable of suppressing bleed-out of a dye generated during a process, A color filter, and an image display apparatus having the color filter.
BACKGROUND ART [0002] Color filters are widely used in imaging elements, liquid crystal displays (LCDs), and the like, and the application range thereof has been expanded. The color filter is usually prepared by uniformly applying a colored photosensitive resin composition containing a pigment corresponding to each color of red, green and blue on a substrate on which a black matrix is pattern-formed, exposing and developing a coating film formed by heating and drying, And repeating an operation of heating and curing as needed, for each color to form pixels of each color.
Korean Patent Laid-Open Publication No. 1998-042233 proposes a radiation-sensitive coloring composition capable of improving the dispersion of a pigment and capable of producing a color filter having a good color contrast, and in addition, Korean Patent Laid-Open Publication No. 1998-080278 proposes a radiation-sensitive coloring composition capable of producing a color filter having good pattern reproducibility.
However, since the pigment is a particle dispersion system, the path of light is shifted due to the refraction and scattering of light, thereby increasing the black luminance and lowering the contrast. Recently, attempts have been made to use dyes having high brightness and excellent heat resistance. The use of only a dye as a coloring agent is preferable because it can realize all the excellent characteristics of a dye, but the use of the dye is limited because the compatibility with other components of the composition is worse than that of the pigment and the color change is large at high temperatures.
Accordingly, a method of using a hybrid type colorant using both a pigment and a dye as colorants has been attempted. However, in the process of applying the overcoat on the color filter and the elution of the dye by the polar solvent used in the process of applying the liquid crystal alignment film There arises a problem that a change in color characteristics occurs, and there is a limitation in use.
It is an object of the present invention to provide a colored photosensitive resin composition capable of inhibiting bleed-out of a dye generated during a process.
Another object of the present invention is to provide a color filter formed using the colored photosensitive resin composition.
It is still another object of the present invention to provide an image display apparatus having the color filter.
1. A colorant comprising (A) an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), wherein the colorant (A) comprises an ionic dye, Soluble resin (B) is polymerized including an amphoteric monomer.
2. The colored photosensitive resin composition according to 1 above, wherein the ionic dye comprises a xanthene dye.
3. The xanthene dye according to claim 2, wherein the xanthene dye is selected from the group consisting of Acid Red 52, Acid Red 289, Rhodamine B, Rhodamine 6G, Food Red 106, Tetramethyl Rhodamine-5-Maleimide, Sulfolodamine B, Rhodamine (19) perchlorate, and at least one selected from the group consisting of rhodamine (19) and perchlorate.
4. The colored photosensitive resin composition according to 1 above, wherein the ionic dye is contained in an amount of 0.1 to 10% by weight based on the total weight of the solid content in the colored photosensitive resin composition.
5. The colored photosensitive resin composition according to 1 above, wherein the amphoteric monomer comprises at least one of the following structures (1) to (4):
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
6. A color filter made of any one of the colored photosensitive resin compositions of any one of items 1 to 5 above.
7. An image display apparatus having the color filter of the above 6.
The colored photosensitive resin composition according to the present invention can inhibit bleed-out of dyes generated during the process by stabilizing an ionic dye by using a polymerized resin containing an amphoteric monomer.
In addition, the color filter manufactured using the colored photosensitive resin composition of the present invention does not cause color mixing and can improve the liquid crystal driving disturbance.
(A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), wherein the colorant (A) comprises an ionic dye, The alkali-soluble resin (B) is polymerized by including an amphoteric monomer, thereby inhibiting bleed-out of a dye generated during the process, and improving color mixing and liquid crystal driving disturbance.
Hereinafter, the present invention will be described in more detail.
≪ Colored photosensitive resin composition &
The colored photosensitive resin composition of the present invention comprises a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E).
The colorant (A)
The colorant (A) according to the present invention essentially comprises an ionic dye.
The ionic dye can be stabilized through interaction with the alkali-soluble resin of the present invention to be described later and effectively inhibit bleed-out during the process.
When a photosensitive resin composition is prepared using a colorant containing an ionic dye, the color characteristic changes due to the elution of the dye by the polar solvent used in the step of applying the overcoat on the color filter and the step of applying the liquid crystal alignment film .
The kind of the ionic dye is not particularly limited, but it is possible to use, for example, a compound classified as a dye in the color index (The Society of Dyers and Colourists) or a known dye described in a dyeing note Examples thereof include xanthene dyes which are aromatic ionic dyes in that they may be dyes having ionic properties in the molecule and excellent in color purity and transmittance.
Examples of the xanthene dye include Acid Red 52, Acid Red 289, Rhodamine B, Rhodamine 6G, Food Red 106, Tetramethyl Rhodamine-5-Maleimide, Sulfolodamine B, And at least one selected from the group consisting of citric acid, citric acid, citric acid, citric acid, citric acid, citric acid and citric acid.
The ionic dye may be contained in an amount of 0.1 to 10% by weight, and preferably 1 to 5% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the ionic dye is contained in the above-mentioned range, the optical property is excellent and a composition stable to poor dissolution can be obtained.
The colorant (A) of the present invention may further comprise dyes, pigments or a mixture thereof other than those ionic dyes known in the art within the scope of the present invention.
Dyes are compounds classified as dyes in the color index (published by The Society of Dyers and Colourists) or known dyes described in dyeing notes (coloring yarn).
Specific examples of the dye include C.I. As solvent dyes,
C.I. Solvent Yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, and 162;
C.I. Solvent Red 8, 45, 49, 122, 125 and 130;
C.I. Solvent Orange 2, 7, 11, 15, 26 and 56;
C.I. Solvent Blue 35, 37, 59 and 67;
C.I. Green dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35 and the like.
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 and 251;
CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 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, , 383, 394, 401, 412, 417, 418, 422 and 426;
C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169 and 173;
CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, , 335 and 340;
C.I. Acid Violet 6B, 7, 9, 17 and 19;
Dyes such as C.I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109.
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 and 141;
CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 and 250;
C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106 and 107;
CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;
C. I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104;
Dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82.
Also, C.I. As a modantoic dye
CI. Modetto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 and 65;
CI Modal Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94 and 95;
C. I. Modanto orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 and 48;
CI Modanito Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 43, 44, 48, 49, 53, 61, 74, 77, 83 and 84;
C. I. Modanth violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58;
Dyes such as C.I. Modatto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53.
As the pigment, a compound classified as a pigment in a color index (published by The Society of Dyers and Colourists) can be used, and it is preferable to use an organic pigment in view of excellent heat resistance and color development.
Specific examples of pigments that can be used in the present invention include,
C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 63, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194 and 214;
C.I. Orange pigments such as Pigment Orange 13, 31, 38, 41, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 264, 265;
C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;
C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C.I. Green pigments such as Pigment Green 7, 36, and 58;
C.I. Brown pigments such as Pigment Brown 23 and 25;
C.I. Pigment black 1, pigment black 7, and the like.
Among these, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Red 177, C.I. Pigment Red 209, C.I. Pigment Red 254, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 6 and C.I. Pigment Green 36. < / RTI >
These pigments may be used alone or in combination of two or more. For example, in order to form red pixels, C.I. Pigment Red 254 and C.I. Pigment Yellow 139, and C.I. Pigment Green 58, C.I. Pigment Yellow 150 or C.I. Pigment Yellow 138, and C.I. Pigment Blue 15: 6.
When the coloring agent comprises a pigment, a pigment dispersion containing the pigment dispersant and performing the dispersion treatment can obtain a pigment dispersion in which the pigment is uniformly dispersed in the solution.
In the present invention, the total solid weight of the colored photosensitive resin composition means the total weight of the components other than the solvent in the colored photosensitive resin composition.
The alkali-soluble resin (B)
The alkali-soluble resin (B) according to the present invention is polymerized including an amphoteric monomer. The amphoteric monomer improves the interaction between the resin and the ionic dye of the present invention by introducing an ionic functional group into the alkali-soluble resin (B) of the present invention, thereby suppressing the elution of the dye generated during the process, . ≪ / RTI >
In one embodiment of the present invention, the amphoteric (betaine) monomer refers to a monomer having both a cation and an anion simultaneously in one molecule.
More specific examples of the amphoteric monomers according to the present invention may include compounds represented by the following general formulas (1) to (4), and from the viewpoints of ease of copolymerization and ease of securing the compounds, Compounds are preferred, but are not limited thereto.
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
The alkali-soluble resin (B) of the present invention can copolymerize the amphoteric monomer with other monomers in order to increase the solubility in a solvent during polymerization and improve the patterning property upon development.
The kind of copolymerizable monomer is not particularly limited, and examples thereof include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene , m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o- vinyl benzyl glycidyl ether, m- Aromatic vinyl compounds such as ether, p-vinylbenzyl glycidyl ether, and indene;
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Acrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Acrylate, isobornyl methacrylate, dicyclopentyl diacrylate, isobornyl methacrylate, isobornyl methacrylate, isobornyl methacrylate, methoxypropyleneglycol methacrylate, methoxypropyleneglycol methacrylate, methoxydipropylene glycol methacrylate, Ethyl acrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxy Acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, unsaturated carboxylic acid esters such as glycerol monoacrylate, glycerol monomethacrylate;
Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl esters;
Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether;
Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide;
Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide;
Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene;
Polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane having a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain Macromonomers, carboxyl group-containing monomers, and the like.
Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids having at least one carboxyl group in the molecule such as unsaturated tricarboxylic acid . Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. The unsaturated polycarboxylic acid may also be mono (2-methacryloyloxyalkyl) ester, and examples thereof include mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) ), Phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be mono (meth) acrylate of the both terminal dicarboxylic polymer, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. have.
These monomers may be used alone or in combination of two or more.
The acid value of the alkali-soluble resin (B) is preferably 20 to 200 (KOH mg / g). When the acid value is in the above range, the solubility in the developer is improved, the non-exposed portion is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed portion remains during development to improve the film remaining ratio. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.
The alkali-soluble resin (B) preferably has a weight average molecular weight (hereinafter simply referred to as "weight average molecular weight") in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluting solvent of 3,000 to 200,000 More preferably from 5,000 to 100,000. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the non-exposed portion in the developer is excellent, and the resolution tends to be improved.
The alkali-soluble resin (B) of the present invention may be used alone or in combination of two or more.
When the compound of the formula (1) is copolymerized with another monomer, the content thereof is not particularly limited. For example, the content of the alkali soluble resin (A) is 10 to 50% by weight, preferably 15 By weight to 40% by weight. When the above range is satisfied, the dye exhibits an appropriate binding force with the ionic dye, and the problem of dissolution of the dye can be effectively suppressed.
The content of the alkali-soluble resin (B) may be 10 to 80% by weight, preferably 20 to 70% by weight based on the total solid weight of the colored photosensitive resin composition of the present invention. When the content of the alkali-soluble resin is within the above range, it can exhibit a proper binding force with the ionic dye, and a pattern can be formed, and the resolution and the residual film ratio are improved.
Photopolymerization The compound (C)
The photopolymerizable compound is not particularly limited as long as it is a compound capable of polymerizing under the action of a photopolymerization initiator (D) described later, but preferably a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound or a trifunctional or higher functional polyfunctional photopolymerizable compound .
Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- And Arylnix M-101 (Doagosei), KAYARAD TC-110S (Nippon Kayaku) or Biscoat 158 (Osaka Yuki Kagaku Kogyo) are commercially available products.
Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) (Acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate. Commercially available products include Aronix M-210, M-1100, 1200 (Doagosei), KAYARAD HDDA (Nippon Kayaku), Viscoat 260 (Osaka Yuki Kagaku Kogyo), AH-600, AT-600 or UA-306H (Kyoeisha Chemical Co., Ltd.).
Specific examples of the polyfunctional photopolymerizable compound having three or more functional groups include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate such as Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku).
Of the photopolymerizable compounds exemplified above, trifunctional or higher (meth) acrylates and urethane (meth) acrylate are particularly preferable because they are excellent in polymerization property and can improve the strength.
The photopolymerizable compounds may be used alone or in combination of two or more.
The photopolymerizable compound is contained in an amount of 5 to 50 mass%, preferably 7 to 45 mass%, based on the total solid content of the colored photosensitive resin composition of the present invention. When the photopolymerizable compound is included in the above range, the strength and smoothness of the pixel portion are good.
Photopolymerization initiator (D)
The photopolymerization initiator can be used without particular limitation as long as it can polymerize the photopolymerizable compound (C).
In particular, the photopolymerization initiator is preferably selected from the group consisting of an acetophenone based compound, a benzophenone based compound, a triazine based compound, a nonimidazole based compound, an oxime compound, and a thioxanthone based compound from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, It is preferable to use at least one compound selected from the group consisting of compounds.
Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1- [4- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-methylcyclohexyl phenyl ketone, 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one -On or 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one. Irgacure 369 (manufactured by CIBA) is a commercially available product.
Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone or 2,4,6-trimethylbenzophenone.
Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 - (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine or 2,4- ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.
Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) , 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) Imidazole compounds in which 4'5,5'-tetraphenyl-1,2'-biimidazole or phenyl groups at 4,4 ', 5,5' positions are substituted by carboalkoxy groups. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.
Specific examples of the oxime compounds include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and commercially available products such as Irgacure OXE-01 (BASF), Irgacure OXE-02 N-1919 (Adeca), NCI-831 (Adeca), and the like are preferable from the viewpoint of curing efficiency, and OXE-02, N-1919 and NCI-831 are preferable.
BASF's OXE-01 and OXE-02 are typical products.
Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone or 1-chloro-4-propanecioxanthone .
Further, within the range not impairing the effect of the present invention, a photopolymerization initiator other than the above-exemplified photopolymerization initiator may be further used. For example, a benzoin compound or an anthracene compound may be used, and these may be used alone or in combination of two or more.
Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, have.
Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid A methyl or a titanocene compound may be further used as a photopolymerization initiator.
The photopolymerization initiator may further include a photopolymerization initiator (D-1) to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention contains a photopolymerization initiation auxiliary (D-1), thereby increasing the sensitivity and improving the productivity.
As the photopolymerization initiation auxiliary (D-1), for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound and an organic sulfur compound having a thiol group can be preferably used.
As the amine compound, an aromatic amine compound is preferably used. Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone ) Or 4,4'-bis (diethylamino) benzophenone.
The carboxylic acid compound is preferably an aromatic heteroacetic acid, and more specifically, it is preferably an aromatic heteroaromatic acid such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine or naphthoxyacetic acid.
Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexaquis (3-mercaptopropionate), or tetraethylene glycol bis (3-mercaptopropionate). .
The photopolymerization initiator (D) may be contained in an amount of 0.1 to 10% by mass based on the solid content of the colored photosensitive resin composition based on the solid content. When the coloring photosensitive resin composition is included in the above-described range, the sensitivity of the colored photosensitive resin composition becomes high, the exposure time is shortened, productivity is improved, and high resolution can be maintained. Further, the strength of the pixel portion formed using the composition of the above-described conditions and the smoothness of the surface of the pixel portion can be improved.
When the photopolymerization initiator (D-1) is further used, it is preferable to use the same content range as the photopolymerization initiator (D). When the photopolymerization initiator is used in the above range, the sensitivity of the colored photosensitive resin composition increases, The productivity of the colored layer formed using the composition can be improved.
Solvent (E)
As long as the solvent (E) is effective for dissolving the other components contained in the colored photosensitive resin composition, the solvent used in the conventional colored photosensitive resin composition can be used without particular limitation, and in particular, an ether, an aromatic hydrocarbon, a ketone, , Esters, amides and the like are preferable.
Specific examples of the solvent include 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 dipropyl ether, di Propylene glycol monomethyl ether, ethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, Ethers such as dipropylene glycol dibutyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Methylcellosolve acetate, ethylcellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxypropionate, methyl 3-methoxypropionate, Methoxybutyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, Lactone, etc. And the like.
The solvent is preferably an organic solvent having a boiling point of 100 占 폚 to 200 占 폚 in terms of coatability and dryness, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, 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.
The solvent may be contained in an amount of 40 to 90 mass%, preferably 50 to 85 mass%, based on the total mass of the colored photosensitive resin composition of the present invention. In the above range, when the resin is coated with a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an inkjet,
Additive (F)
The colored photosensitive resin composition of the present invention may further contain at least one additive selected from the group consisting of a dispersant, another polymer compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti-
≪ Color filter and image display device >
The present invention provides a color filter manufactured using the colored photosensitive resin composition and an image display apparatus provided with the color filter.
The image display device having such a color filter may be a liquid crystal display device, an OLED, a flexible display, or the like, but is not limited thereto and all applicable image display devices known in the art are applicable.
The color filter can be produced by applying the above-mentioned colored photosensitive resin composition of the present invention on a substrate, and photo-curing and developing it to form a pattern.
First, the colored photosensitive resin composition is coated on a substrate and then heated and dried to remove volatile components such as a solvent to obtain a smooth coated film.
The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coating method, a slit coating method, or the like. After application, heating and drying (prebaking), or drying under reduced pressure, volatile components such as solvents are volatilized. Here, the heating temperature is usually 70 to 200 占 폚, preferably 80 to 130 占 폚. The thickness of the coating film after heat drying is usually about 1 to 8 mu m. Ultraviolet rays are applied to the thus obtained coating film through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper to uniformly irradiate a parallel light beam onto the entire exposed portion and accurately align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured.
The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto. The desired pattern shape can be formed by dissolving the unexposed portion and developing the coated film after the hardening is brought into contact with the developing solution.
The developing method may be any of a liquid addition method, a dipping method, and a spraying method. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or an organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , Sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, and the like.
These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass.
The surfactant in the alkali 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 surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.
Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.
Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. Each of 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, and more preferably 0.1 to 5% by mass. After development, it may be washed with water and, if necessary, subjected to post-baking at 150 to 230 ° C for 10 to 60 minutes.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to be illustrative of the present invention and not to limit the scope of the claims appended hereto. It will be obvious to those skilled in the art that such variations and modifications are within the scope of the appended claims.
Manufacturing example 1: Preparation of alkali-soluble resin
A solution prepared by dissolving 40 parts by weight of methacrylic acid, 40 parts by weight of benzylmethacrylate and 20 parts by weight of the monomer of Formula 1 in 150 g of propylene glycol monomethyl ether acetate was heated to 75 DEG C under nitrogen flow, AIBN (0.1 g) And then reacted at the same temperature for 5 hours. Further, AIBN (0.3 g) was added and reacted at the same temperature for 5 hours. Then, 10 parts by weight of glycidyl methacrylate was added and reacted at the same temperature for 2 hours, And cooled to room temperature to obtain an acrylic copolymer having a weight average molecular weight of 85,000.
Manufacturing example 2: Preparation of alkali-soluble resin
An acrylic copolymer (molecular weight: 8.5 million) was prepared in the same manner as in Preparation Example 1, except that the monomer of Formula 2 was used instead of the monomer of Formula 1.
Manufacturing example 3: Preparation of alkali-soluble resin
An acrylic copolymer (molecular weight: 8.5 million) was prepared in the same manner as in Preparation Example 1, except that the monomer of Formula (3) was used in place of the monomer of Formula (1).
Manufacturing example 4: Preparation of alkali-soluble resin
An acrylic copolymer (molecular weight: 8.5 million) was prepared in the same manner as in Preparation Example 1, except that the monomer of Formula 4 was used instead of the monomer of Formula 1.
Manufacturing example 5: Preparation of alkali-soluble resin
40 parts by weight of methacrylic acid, 40 parts by weight of benzylmethacrylate, and 20 parts by weight of each of the compounds of Formula 1 or 2 were replaced by 50 parts by weight of methacrylic acid and 50 parts by weight of benzylmethacrylate, To prepare an acrylic copolymer.
Example 1 to 9 and Comparative Example 1 to 3: Preparation of colored photosensitive resin composition and color filter
As shown in Table 1 below, each of the components was mixed to prepare a colored photosensitive resin composition (unit: g).
The compound (C)
Initiator (D)
A-1: Acid Red 52
A-2: Rhodamine B
A-3: Rhodamine 6G
A-4: Acid Red 289
A-5: methyl red (non-ionic azo dye)
B: alkali-soluble resin
B-1: Production Example 1 Resin
B-2: Preparation Example 2 Resin
B-3: Preparation Example 3 Resin
B-4: Production Example 4 Resin
B-5: Production Example 5 Resin
C: dipentaerythritol hexaacrylate (Kayarad DPHA: manufactured by Nippon Kayaku Co., Ltd.)
D: Irgacure 369 (CIBA)
E: Propylene glycol monomethyl ether acetate
A color filter was prepared using the colored photosensitive resin compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3. Specifically, each of the colored photosensitive resin compositions was coated on a glass substrate by spin coating, then placed on a heating plate, and held at a temperature of 100 캜 for 3 minutes to form a thin film. Then, a test photomask having a line / space pattern of 1 mu m to 50 mu m was placed on the thin film and irradiated with ultraviolet rays at a distance of 100 mu m from the test photomask. At this time, the ultraviolet light source was irradiated with a high pressure mercury lamp of 1 KW containing g, h and i lines at an illuminance of 100 mJ / cm 2, and no special optical filter was used. The ultraviolet-irradiated thin film was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220 ° C for 1 hour to prepare a color filter. The film thickness of the color filter prepared above was 2.0 탆.
Experimental Example 1: Dissolution test of dye
Each of the color filters prepared in Examples 1 to 9 and Comparative Examples 1 to 3 was cut into a size of 5 cm x 1 cm and then immersed in 16 ml of NMP (N-methylpyrolidone) solution at 80 ° C for 40 minutes, The absorbance was measured by the spectrum and the results are shown in Table 2 below. It is generally judged that the elution of the dye is suppressed when the absorbance is 0.3 or less.
Referring to Table 2, it can be seen that the examples (Examples 1 to 7) comprising the alkali-soluble resin copolymerized with the amphoteric monomers of the present invention inhibit the elution of the dye, so that the absorbance of the NMP extraction solution is low . However, it can be seen that the absorbance of Examples 8 to 9, in which the content of the dye is rather excessive, was measured to be somewhat higher.
However, in Comparative Example 1 using an alkali-soluble resin copolymerized with no amphoteric monomer, Comparative Example 2 using no ionic dye, and Comparative Example 3 using neither an ionic dye nor an amphoteric monomer, the absorbance Was measured very high.
Claims (7)
Wherein the colorant (A) comprises an ionic dye,
The alkali-soluble resin (B) is obtained by polymerizing an amphoteric monomer.
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140029648A KR20150107156A (en) | 2014-03-13 | 2014-03-13 | Colored Photosensitive Resin Composition and Color Filter Comprising the Same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140029648A KR20150107156A (en) | 2014-03-13 | 2014-03-13 | Colored Photosensitive Resin Composition and Color Filter Comprising the Same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20150107156A true KR20150107156A (en) | 2015-09-23 |
Family
ID=54245720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020140029648A KR20150107156A (en) | 2014-03-13 | 2014-03-13 | Colored Photosensitive Resin Composition and Color Filter Comprising the Same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20150107156A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190034312A (en) * | 2016-08-01 | 2019-04-01 | 메르크 파텐트 게엠베하 | Photosensitive composition, color conversion medium, optical device and manufacturing method thereof |
| JP2019066737A (en) * | 2017-10-03 | 2019-04-25 | 東洋インキＳｃホールディングス株式会社 | Color filter coloring composition and color filter |
| JP2019109490A (en) * | 2017-12-15 | 2019-07-04 | 東洋インキＳｃホールディングス株式会社 | Colored composition for color filter, and color filter |
| CN110997624A (en) * | 2017-06-06 | 2020-04-10 | 韦恩州立大学 | Methods and compositions related to carnitine-derived materials |
-
2014
- 2014-03-13 KR KR1020140029648A patent/KR20150107156A/en not_active Application Discontinuation
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190034312A (en) * | 2016-08-01 | 2019-04-01 | 메르크 파텐트 게엠베하 | Photosensitive composition, color conversion medium, optical device and manufacturing method thereof |
| CN110997624A (en) * | 2017-06-06 | 2020-04-10 | 韦恩州立大学 | Methods and compositions related to carnitine-derived materials |
| JP2020522534A (en) * | 2017-06-06 | 2020-07-30 | ウェイン ステート ユニバーシティＷａｙｎｅ Ｓｔａｔｅ Ｕｎｉｖｅｒｓｉｔｙ | Methods and compositions for carnitine-derived materials |
| EP3634942A4 (en) * | 2017-06-06 | 2021-03-10 | Wayne State University | Methods and compositions relating to carnitine- derived materials |
| US11103588B2 (en) * | 2017-06-06 | 2021-08-31 | Wayne State University | Methods and compositions relating to carnitine-derived materials |
| US11591287B2 (en) | 2017-06-06 | 2023-02-28 | Wayne State University | Antifouling zwitterionic polymer coating and reverse coating method |
| JP2019066737A (en) * | 2017-10-03 | 2019-04-25 | 東洋インキＳｃホールディングス株式会社 | Color filter coloring composition and color filter |
| JP2019109490A (en) * | 2017-12-15 | 2019-07-04 | 東洋インキＳｃホールディングス株式会社 | Colored composition for color filter, and color filter |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI675254B (en) | Blue photosensitive resin composition, blue color filter and display device having the same | |
| KR20150025674A (en) | A colored photosensitive resin composition | |
| KR20150107156A (en) | Colored Photosensitive Resin Composition and Color Filter Comprising the Same | |
| TWI767904B (en) | Colored photosensitive resin composition and color filter comprising the same | |
| TW201736950A (en) | Colored photosensitive resin composition and column spacer comprising the same | |
| KR20150051446A (en) | A colored photosensitive resin composition | |
| CN111752103B (en) | Red photosensitive resin composition and color filter comprising same | |
| KR20150010071A (en) | A colored photosensitive resin composition, color filter and display device comprising the same | |
| KR20180007808A (en) | Colored photosensitive resin composition, color filter and image display device produced using the same | |
| KR20150106665A (en) | A colored photosensitive resin composition | |
| CN110244512B (en) | Red photosensitive resin composition and color filter comprising same | |
| KR102195690B1 (en) | Photosensitive resin comopsition, photocurable pattern formed from the same and image display comprising the pattern | |
| KR20040065163A (en) | Photosensitive resin composition | |
| KR101917406B1 (en) | Photosensitive resin composition, color filter with high color reproducing and liquid crystal display device using the same | |
| KR20150072084A (en) | Colored Photosensitive Resin Composition and Color Filter Comprising the Same | |
| KR102024868B1 (en) | A colored photosensitive resin composition, color filter and display device comprising the same | |
| KR102017246B1 (en) | Polyfunctional acrylate compounds, a colored photosensitive resin, color filter and display device comprising the same | |
| KR101861067B1 (en) | Black photosensitive resin composition | |
| KR20180052372A (en) | Photosensitive Resin Composition, Color Filter and Display Device | |
| KR101401488B1 (en) | Colored photosensitive resin composition, and color filter and liquid crystal display device prepared by using the same | |
| KR20150107083A (en) | Colored photosensitive resin composition and color filter using the same and image display device comprising the color filter | |
| KR20150107162A (en) | Colored photosensitive resin composition and color filter using the same and image display device comprising the color filter | |
| KR20160115190A (en) | Colored photosensitive resin composition | |
| KR20220001962A (en) | A photosensitive resin composition for forming partition wall, a partition wall for a color conversion layer, a color conversion layer comprising the partition wall, and an image display device comprising the color conversion layer | |
| KR20160112645A (en) | Colored photosensitive resin composition and color filter using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WITN | Withdrawal due to no request for examination |