KR20150109106A - A colored photosensitive resin composition for color filter, color filter and liquid crystal display device having the same - Google Patents
A colored photosensitive resin composition for color filter, color filter and liquid crystal display device having the same Download PDFInfo
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- KR20150109106A KR20150109106A KR1020140032144A KR20140032144A KR20150109106A KR 20150109106 A KR20150109106 A KR 20150109106A KR 1020140032144 A KR1020140032144 A KR 1020140032144A KR 20140032144 A KR20140032144 A KR 20140032144A KR 20150109106 A KR20150109106 A KR 20150109106A
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- 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
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- 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
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/23—Photochromic filters
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- 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
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- 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
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- 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
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- 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
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- 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
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- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
The present invention relates to a colored photosensitive resin composition, a color filter, and a liquid crystal display device having the same.
Background Art [0002] A color filter is widely used for a plasma display panel (PDP), a liquid crystal display (LCD), a field emission display (FEL), and a light emitting display (LED), and its application range is rapidly expanding. Particularly, in recent years, the use of the liquid crystal display (LCD) has been further expanded, and accordingly, the color filter has been recognized as one of the most important components in reproducing the color tone of the LCD.
In recent years, the concentration of the coloring agent in the colored photosensitive resin composition used for the production of the color filter has been continuously increasing to achieve high color purity, and a method of simultaneously using the pigment and the dye as the coloring agent has been studied. On the other hand, there is a demand for a colored photosensitive resin composition having a high developing speed and excellent sensitivity and reliability even at a low exposure dose in order to improve process productivity and yield.
Meanwhile, dipentaerythritol hexaacrylate (hereinafter referred to as DPHA) is used as a monomer for forming a color filter for a liquid crystal display (LCD), for example, as a photopolymerizable compound contained in the composition And conventionally, a composition containing only DPHA has been used (for example, see Japanese Unexamined Patent Application Publication No. 8-271723).
However, when only DPHA is used, there is a problem that the composition to be removed by the alkali developing solution at the time of development remains on the substrate as a residue.
In recent years, there has been a strong demand for a high coloring density and thinning of a color filter in order to improve the image quality due to the high condensing property and the high color separability of a solid-state image pickup device such as a CCD.
Thus, conventionally, a large amount of a coloring material is added to a resist for a high coloring density, which further lowers the alkalinity developing property and makes it impossible to remove the residue of the unexposed portion.
On the other hand, Korean Patent Laid-Open No. 10-2009-0113780 discloses a composition which exhibits a high sensitivity and forms a good pattern in an alkali form by using a specific photopolymerizable compound, but the above- There is a problem in that the adhesive strength and tinting strength are deteriorated.
SUMMARY OF THE INVENTION The present invention has been made to overcome the problems of the prior art, and it is an object of the present invention to provide a colored photosensitive resin composition capable of obtaining a pixel having a high contrast ratio.
Another object of the present invention is to provide a colored photosensitive resin composition which is excellent in sensitivity and adhesion while maintaining a developing speed, free from peeling of a pattern during a development process, and excellent in solvent resistance, heat resistance and hardness.
The present invention relates to a colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E)
Wherein the colorant (A) comprises at least one pigment (a1) and at least one dye (a2)
Wherein the photopolymerizable compound (C) comprises a compound represented by the following general formula (1).
In Formula 1,
R are, each independently, a hydrogen (-H) or a methyl group (-CH 3) and;
m and n are equal to each other and are 1 or 2;
The present invention also provides a color filter made of the colored photosensitive resin composition.
Further, the present invention provides a liquid crystal display device including the color filter.
The colored photosensitive resin composition of the present invention has an advantage of being excellent in sensitivity and adhesion while maintaining a developing speed, free of pattern peeling during the development process, and excellent in solvent resistance, heat resistance and hardness.
Hereinafter, the present invention will be described in more detail.
The conventional colored photosensitive composition has a problem that the composition to be removed by the alkali developing solution at the time of development remains on the substrate as a residue and the coloring power is inferior due to insufficient photopolymerization density.
In order to solve this problem, the inventors of the present invention have found that by including a photopolymerizable compound (C) containing a compound of the following formula (1), it is possible to provide a photosensitive composition which is excellent in sensitivity and adhesion while maintaining a developing speed, Hardness is excellent, and the present invention has been completed.
The present invention relates to a colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E)
Wherein the colorant (A) comprises at least one pigment (a1) and at least one dye (a2)
The photopolymerizable compound (C) provides a colored photosensitive resin composition comprising a compound represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
R are, each independently, a hydrogen (-H) or a methyl group (-CH 3) and;
m and n are equal to each other and are 1 or 2;
Each component constituting the colored photosensitive resin composition of the present invention will be described below.
First, the colorant (A) will be described.
The colorant (A) contains at least one pigment (a1) and at least one dye (a2) as essential components.
The pigment (a1)
The pigment may be an organic pigment or an inorganic pigment generally used in the art.
The organic pigments may be various pigments used in printing ink, ink jet ink, etc. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, An anthanthrone pigment, an indanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, a pyranthrone pigment, A pyranthrone pigment, a diketopyrrolopyrrole pigment, and the like.
The arms can be exemplified by metal compounds such as the pigment as the metal oxides, metal complex salts, specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, an oxide of a metal such as carbon black Or composite metal oxides.
In particular, the as organic pigments and inorganic pigments can include compounds that are classified as pigments in the particular color index (The society of Dyers and Colourists Publishing), more specifically, the color index (CI) numbers as described below Pigments, but are not limited thereto.
C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185
C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71
C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264
C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38
C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76
C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58
C.I Pigment Brown 28
C.I Pigment Black 1 and 7, etc.
The exemplified C.I. Among the pigment pigments, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment selected from Pigment Green 58 can be preferably used.
The above-mentioned pigments may be organic pigments or inorganic pigments generally used in the art. These pigments may be used alone or in combination of two or more.
It is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment includes a method of dispersing the pigment dispersion (a3) by containing the pigment dispersant (a3). According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained have.
The pigment dispersant (a3)
The pigment dispersant (a3) is added to maintain deactivation and stability of the pigment and may be any of those generally used in the art without limitation, and examples thereof include cationic, anionic, nonionic, amphoteric, polyester , Polyamine-based surfactants, and the like.
(Hereinafter referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate). At this time, it is preferable to apply the acrylic dispersant prepared by a living control method as disclosed in Korean Patent Laid-Open Publication No. 2004-0014311. DISCLOSURE OF INVENTION It is an object of the present invention to provide an acrylic dispersant, 2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.
The acrylic dispersants exemplified above may be used alone or in combination of two or more.
As the pigment dispersant (a3), other resin type pigment dispersants other than the acrylic dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine 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 ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters.
In addition to the above acrylic dispersant, other resin type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylic dispersant.
The amount of the pigment dispersant (a3) to be used is in the range of 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (a1). If the content of the pigment dispersant (a3) exceeds 60 parts by weight based on the above-mentioned criteria, the viscosity may be increased. If the content of the pigment dispersant is less than 5 parts by weight, it may be difficult to atomize the pigment or gelation after dispersion.
The dye (a2)
The dye (a2) may be used without limitation as long as it has solubility in an organic solvent. It is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility in an alkali developing solution, heat resistance and solvent resistance.
Examples of the dye include acid dyes having an acidic group such as sulfonic acid and carboxylic acid, salts of an acidic dye and a nitrogen-containing compound, sulfonamides of an acidic dye and derivatives thereof, and azo, xanthan, Phthalocyanine-based acid dyes and derivatives thereof can also be selected.
Preferably, the dye is a compound classified as a dye in the color index (published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (coloring yarn).
Specific examples of the dye include C.I. As solvent dyes,
C.I. Yellow dyes such as Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163;
C.I. Red dyes such as Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;
C.I. Orange dyes such as solvent orange 2, 7, 11, 15, 26, 41, 45, 56, 62;
C.I. Blue dyes such as Solvent Blue 5, 35, 36, 37, 44, 59, 67 and 70;
C.I. Violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49;
C.I. Green dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and the like.
Among them, C.I. Solvent dye having excellent solubility in an organic solvent. Solvent Yellow 14, 16, 21, 56, 151, 79, 93; C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Orange 41, 45, 62; C.I. Solvent Blue 35, 36, 44, 45, 70; C.I. Solvent violet 13 is preferred, and C.I. Solvent Yellow 21, 79; C.I. Solvent Red 8, 122, 132; C.I. Solvent orange 45, 62 is more preferable.
Also, C.I. As an acid dye
CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 Yellow dyes such as 1,1,1,2,2,2,2,2,2,23,28, 240,242, 243,251 and the like, such as, for example, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, ;
CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 Red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 426;
Orange dyes such as C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, , 335, 340 and the like;
Violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19, 66 and the like;
Green dyes such as C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106,
Among them, CI Acid Yellow 42, which is excellent in solubility in organic solvents among acid dyes; C.I. Acid Red 92; C. I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27 is preferred.
As a C.I. direct dye,
CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , Yellow dyes such as 136, 138, and 141;
CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Orange dyes such as C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;
Violet dyes such as C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
Green dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79,
Also, C.I. As a modantoic dye
Yellow dyes such as C.I. Modatto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
CI Modal Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, Red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
CI Modanato Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, dyes;
CI Modanito Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 43, 44, 48, 49, 53, 61, 74, 77, 83, and 84;
Violet colored dyes such as C.I. Modanth violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Green dyes such as C.I. Modatto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43,
In the present invention, the dyes (a2) may be used alone or in combination of two or more.
According to a preferred embodiment of the present invention, the content of the colorant (A) is preferably 5 to 60% by weight, more preferably 10 to 45% by weight based on the total solid content in the colored photosensitive resin composition of the present invention .
When the colorant (A) is contained in an amount of 5 to 60% by weight on the basis of the above criteria, the color density of the pixel is sufficient even when a thin film is formed, and the residue of the non- .
In the present invention, the total solid content in the colored photosensitive resin composition means the total content of the remaining components excluding the solvent from the colored photosensitive resin composition.
The alkali-soluble resin (B)
Is copolymerized with an ethylenically unsaturated monomer (b1) having a carboxyl group as an essential component in order to obtain solubility in an alkali developing solution used in a development processing step for forming a pattern.
Specific examples of the ethylenically unsaturated monomer (b1) having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids; ω-carboxypolycaprolactone mono (meth) acrylate, and the like. Of these, acrylic acid and methacrylic acid are preferred. Among these, mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals are preferred.
In order to ensure compatibility with the dye (a2) and storage stability of the colored photosensitive resin composition of the present invention, the acid value of the alkali-soluble resin (B) is preferably 30 to 150 mgKOH / g.
When the acid value of the alkali-soluble resin (B) is less than 30 mgKOH / g, it is difficult to ensure a sufficient developing rate of the colored photosensitive resin composition. When the acid value exceeds 150 mgKOH / g, the adhesion with the substrate is decreased, , The dye in the colored photosensitive resin composition is precipitated or the storage stability of the colored photosensitive resin composition is lowered, and the viscosity tends to rise.
In addition, the alkali-soluble resin (B) of the present invention may be given a hydroxyl group in order to secure further developability. However, the sum of the hydroxyl value of the alkali-soluble resin (B) and the photopolymerizable compound (C) is limited to 50 mgKOH / g or more and 250 mgKOH / g or less. When the sum of the hydroxyl groups is less than 50 mgKOH / g, a sufficient developing rate can not be secured. When it exceeds 250 mgKOH / g, the dimensional stability of the formed pattern is lowered and the linearity of the pattern becomes poor and the compatibility with the dye is deteriorated A problem of storage stability tends to occur.
(B1) having a carboxyl group and an ethylenically unsaturated monomer (b2) having a hydroxyl group may be copolymerized with an ethylenically unsaturated monomer (b1) having a carboxyl group to give a hydroxyl group to the alkali-soluble resin (B) ) With a glycidyl group-containing compound (b3). (B3) having a glycidyl group in addition to a copolymer of an ethylenically unsaturated monomer (b1) having a carboxyl group and an ethylenically unsaturated monomer (b2) having a hydroxyl group.
Specific examples of the butylenically unsaturated monomer (b2) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxy-3-phenoxypropyl (meth) acrylate, N-hydroxyethylacrylamide and the like. Of these, 2-hydroxyethyl (meth) acrylate is preferable, and the above-described butyrylenically unsaturated monomer (b2) may be used in combination of two or more.
Specific examples of the glycidyl group-containing compound (b3) include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, Ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, aryl glycidyl ether, Among them, butyl glycidyl ether, aryl glycidyl ether and methacrylic acid glycidyl ester are preferable, and the glycidyl group-containing compound (b3) described above is used in combination of two or more kinds Can be used.
On the other hand, the unsaturated monomers (b3) which can be copolymerized in the production of the alkali-soluble resin (B) are illustrated below but are not limited thereto.
In addition to the ethylenically unsaturated monomer (b2) having a hydroxyl group and the compound (b3) having a glycidyl group in the ethylenically unsaturated monomer (b1) having a carboxyl group in the production of the alkali-soluble resin (B) (b4) may be copolymerized.
The kind of the copolymerizable unsaturated monomer (b4) is illustrated below but is not limited thereto.
Specific examples of the polymerizable monomer (b4) having an unsaturated bond capable of copolymerization include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- Aromatic vinyls such as vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m- vinyl benzyl glycidyl ether and p- compound;
N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm -phenyl maleimide, phenyl maleimide Np-, No- methoxyphenyl maleimide, Nm- methoxyphenyl maleimide, Np- methoxy-N- substituted maleimide-based compounds such as phenyl maleimide;
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; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- 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) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds.
The monomers exemplified as the copolymerizable unsaturated monomer (b4) may be used alone or in combination of two or more.
The content of the alkali-soluble resin (B) should satisfy the condition that the sum of the hydroxyl value of the alkali-soluble resin (B) and the photopolymerizable compound (C) is from 50 mgKOH / g to 250 mgKOH / g. May be in the range of 5 to 80% by weight, preferably 10 to 70% by weight, based on the total solid content. When the content of the alkali-soluble resin (B) is 5 to 80% by weight on the basis of the above-mentioned criteria, the solubility in a developing solution is sufficient and pattern formation is easy, and film reduction of the pixel portion of the exposed portion is prevented during development, It is preferable that the dropout property is improved.
The photopolymerization compound (C)
According to a preferred embodiment of the present invention, there is provided a photopolymerizable compound (C) comprising a carboxylic acid anhydride modified epoxy acrylate represented by the following general formula (1).
[Chemical Formula 1]
In Formula 1,
R are, each independently, a hydrogen (-H) or a methyl group (-CH 3) and;
m and n are equal to each other and are 1 or 2;
The photopolymerizable compound (C) of the present invention is excellent in sensitivity and adhesion while maintaining the developing rate, and has no peeling of the pattern during the development process, and is excellent in solvent resistance, heat resistance and hardness.
The photopolymerizable compound (C) is a compound capable of polymerizing under the action of the photopolymerization initiator (D) described below, and can be used in combination with a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound or a trifunctional or higher functional photopolymerizable compound A multifunctional monomer having two or more functional groups can be used.
Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- But are not limited thereto. Commercially available products include Aronix M-101 (Doagosei), KAYARAD TC-110S (Nippon Kayaku), and Viscot 158 (Osaka Yuki Kagaku Kogyo) .
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, 3-methylpentanediol di (meth) acrylate, and the like, but not limited thereto. Commercially available products include Aronix M-210, M-1100, KAYARAD HDDA (Nippon Kayaku), Biscoat 260 (Osaka Yuki Kagaku Kogyo), AH-600, AT-600 and UA-306H (Kyoeisha Chemical Co., Ltd.).
According to a preferred embodiment of the present invention, examples of the trifunctional or more polyfunctional photopolymerizable compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylate Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol (Meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Commercially available products include Aronix M-309, TO-1382 KAYARAD TMPTA, KAYARAD DPHA, and KAYARAD DPHA-40H (Nippon Kayaku), and the like. However, the (meth) acrylic esters and the urethane (meth) And it is particularly preferred in that it can improve the strength.
According to a preferred embodiment of the present invention, when used in combination with the photopolymerizable compound (C) containing the compound of formula (1), it is preferable to use 80% or less of the total photopolymerizable compound (C). If it is used in excess of 80%, the performance of the photopolymerizable compound (C) is hardly realized.
More specifically, the photopolymerizable compound (C) is preferably contained in an amount of 5 to 80% by weight, more preferably 20 to 60% by weight based on the solid content in the colored photosensitive resin composition of the present invention.
When the photopolymerizable compound (C) is contained in an amount of 20 to 60% by weight based on the above-mentioned criteria, the strength and smoothness of the pixel portion are preferably improved.
Photopolymerization initiator (D)
The photopolymerization initiator (D) is preferably an oxime ester-based photopolymerization initiator (d1) having a structure represented by the following formula (2).
In the formula 2, R 1 is represented by the following formula 3, R 4 in the formula 3 may be a C 1 -C 4 alkylene, R 5 may be a C 3 -C 8 alkyl, a C 3 -C 8 cycloalkyl or a C 6 -C 8 aromatic hydrocarbon, R2 in the above formula (2) may be C1-C8 alkyl, phenyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl group, and R3 may be a substituted or unsubstituted diphenylsulfide group.
The photopolymerization initiator (d1), which is a structure of the above formula (2), prevents photodecomposition due to the dye, and thus exhibits effective photopolymerization properties in a colored photosensitive resin composition containing a dye as a colorant.
Examples of the photopolymerization initiator (d1) of Formula 2 include TR-PBG-305 and OXE-01.
In addition, the photopolymerization initiator (d2) other than those described above may be further used in combination within the range not impairing the effects of the present invention. Typically, it is preferable to use at least one compound selected from the group consisting of an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a nonimidazole-based compound, and a thioxanthone-based compound.
The specific examples of the acetophenone based compounds is diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-methylcyclohexyl phenyl ketone, 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.
Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.
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, 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- , 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.
Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .
The photopolymerization initiator (D) may further include a photopolymerization initiator (d3) 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 (d3), whereby the sensitivity is further increased and the productivity can be improved.
As the photopolymerization initiation assistant (d3), 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 ), 4,4'-bis (diethylamino) benzophenone, and the like.
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, naphthoxyacetic acid and the like.
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 hexacis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) .
According to a preferred embodiment of the present invention, the photopolymerization initiator (D) is used in an amount of 0.1 to 40 parts by weight, preferably 1 to 40 parts by weight, based on 100 parts by weight of the sum of the alkali-soluble resin (B) 30 parts by weight. When the amount of the photopolymerization initiator (D) is in the range of 0.1 to 40 parts by weight, the colored photosensitive resin composition is highly sensitized and the exposure time is shortened, which is preferable because 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. In the case of the photopolymerization initiator (d1), which is a structure of the general formula (2), 10 to 100% by weight, preferably 20 to 100% by weight, of the total photopolymerization initiator should be included. When the ratio of the photopolymerization initiator (d1), which is the structure of the above formula (2), is less than 10% by weight, the sensitivity of the dye can not be overcome and the pattern is likely to be short-circuited during the development process.
When the photopolymerization initiator (d3) is further used, the photopolymerization initiator (d3) is added in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the sum of the alkali-soluble resin (B) , Preferably 1 to 30 parts by weight.
When the amount of the photopolymerization initiator (d3) used is within the range of 0.1 to 40 parts by weight, the sensitivity of the colored photosensitive resin composition is higher and the productivity of the color filter formed using the composition is improved.
Solvent (E)
As long as the solvent (E) is effective for dissolving other components contained in the colored photosensitive resin composition, a solvent used in a conventional colored photosensitive resin composition can be used without particular limitation, and in particular, an ether, an aromatic hydrocarbon, Alcohols, esters, amides and the like are preferable.
The solvent (E) specifically includes ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as? -Butyrolactone; And the like.
The solvent (E) is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C in terms of coatability and drying property, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate Tartrate, butylacetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.
The above-mentioned solvents (E) may be used alone or in admixture of two or more. The solvent (E) may include 60 to 89.99% by weight, preferably 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition of the present invention have.
When the above-mentioned solvent (E) is in the range of 60 to 89.99% by weight, when it is coated with a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater Thereby providing an effect of improving the property.
Additive (F)
The additive (F) may be optionally added, for example, other polymer compounds, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an antiflocculant.
Specific examples of the other polymer compound include a curable resin such as epoxy resin and maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane and the like .
The curing agent is used for deep curing and for increasing mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.
Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides and isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.
Specific examples of the oxetane compound in the curing agent include carbonates bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like.
The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. The curing assistant compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agent include epoxy resin curing agents such as epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, Manufactured by Japan Ehwa Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.
The surfactant may be used to further improve film-forming properties of the photosensitive resin composition, and a fluorine-based surfactant or a silicone-based surfactant may be preferably used.
Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 from Dow Corning Toray Silicone Co., Ltd. and TSF-4440, TSF-4300, TSF-4445, TSF-4446 and TSF-4460 , And TSF-4452. Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated. The above-exemplified surfactants may be used alone or in combination of two or more.
Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the solid content of the colored photosensitive resin composition.
Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.
Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.
The present invention also provides a color filter made of the colored photosensitive resin composition.
Further, the present invention provides a liquid crystal display device including the color filter.
The process for producing the colored photosensitive resin composition of the present invention will be described as follows.
First, one or more pigments (a1) to (a2) of the colorant (A) are mixed with a solvent (E) and, if necessary, a pigment dispersant (a3) or an alkali-soluble resin (B) , Dissolve or disperse.
(B), the photopolymerizable compound (C) and the photopolymerization initiator (D) and, if necessary, the additive (F) and the solvent (E) are further added to the mixed solution so as to have a predetermined concentration, A colored photosensitive resin composition can be produced.
Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are on a mass basis unless otherwise specified.
Synthesis Example 1 : Synthesis of alkali-soluble resin (B, solid content 60% by weight)
A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 19.0 parts by weight of acrylic acid, 10 parts by weight of the reaction product, 51.0 parts by weight of styrene and 3 parts by weight of n-dodecylmercaptan were charged and replaced with nitrogen. Thereafter, the temperature was elevated to 110 DEG C with stirring, and the reaction was carried out for 6 hours. Subsequently, the temperature of the reaction solution was lowered to room temperature, the air in the flask was replaced with ordinary air, and then 0.3 parts by weight of triethylamine and 20 parts by weight of glycidyl methacrylate were added thereto and reacted at 110 DEG C for 5 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 80 mgKOH / g and a weight average molecular weight Mw of about 22,000 as measured by GPC.
Synthesis Example 2 : Pigment dispersion composition M
12 parts by weight of CI Pigment Blue 15: 6 (pigment), 1.8 parts by weight of CI Acid Red 52, 4.0 parts by weight of BYK-2001 as a pigment dispersant and 82.2 parts by weight of propylene glycol monomethyl ether acetate were mixed, And then mixed and dispersed in a mill for 12 hours to prepare a pigment dispersion M.
Preparation of colored photosensitive resin composition
Example One
(A) a pigment dispersion composition M; 100 parts by weight
(B) 19.8 parts by weight of the resin (B) of Synthesis Example 1,
(C) Polymerizable compound of formula (4): 6.6 parts by weight (product name: EA-6340 / PGMAC, Shin Nakamura)
(D) Polymerization initiator: 1.3 parts by weight of PBG-305 (manufactured by Troni) as an oxime ester-based initiator
(E) Solvent: Propylene glycol monomethyl ether acetate 52.7 parts by weight
Were mixed to prepare a colored curable resin composition.
Example 2
A colored photosensitive resin composition was prepared in the same manner as in Example 1, except that the following compound (C) was used.
(C) Polymerizable compound of formula (5): 6.6 parts by weight (product name: EA-7140 / PGMAC, Shin Nakamura)
Comparative Example One
A colored photosensitive resin composition was prepared in the same manner as in Example 1, except that the following compound (C) was used.
(C) Polymerizable compound of formula (6): 6.6 parts by weight (product name: EA-5321, Shin Nakamura)
Comparative Example 2
A colored photosensitive resin composition was prepared in the same manner as in Example 1, except that the following compound (C) was used.
(C) Polymerizable compound of formula (7): 6.6 parts by weight (product name: EA-5323, Shin Nakamura)
Comparative Example 3
A colored photosensitive resin composition was prepared in the same manner as in Example 1, except that the following compound (C) was used.
(C) Polymerizable compound of formula (8): 6.6 parts by weight (product name: EA-5521, Shin Nakamura)
m = n = 1
m = n = 2
Manufacturing example : Color filter ( Glass Board)
A color filter was prepared using the colored photosensitive resin compositions prepared in Examples 1 to 2 and Comparative Examples 1 to 3. That is, each of the colored photosensitive resin compositions was coated on a glass substrate by spin coating, and then placed on a heating plate and held at a temperature of 100 ° C for 3 minutes to form a thin film. Then, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% in a stepwise manner and a line / space pattern of 1 to 50 m was placed on the thin film and an interval of 100 m from the test photomask was measured. Respectively. 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 thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate on which the thin film was coated was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C for 20 minutes to prepare a color filter. The average thickness of the film of the color filter prepared above was 2.0 탆.
Experimental Example One
The developing speed, adhesion, solvent resistance, heat resistance and hardness of the color filter prepared in the above Production Example were measured and evaluated as follows, and the results are shown in Table 1 below.
≪ Development speed >
The time taken for the unexposed area to completely dissolve in the developing solution at the time of development was measured.
≪ Adhesion >
When the generated pattern was evaluated through an optical microscope, the following pattern was evaluated as a degree of peeling phenomenon.
○: No pattern peeling
△: 1 to 3 pattern peeling
X: Pattern peeling 4 or more
<Solvent resistance>
The prepared color filter was immersed in an N-methylpyrrolidone solvent for 30 minutes to compare and evaluate the color change before and after the evaluation. The equation to be used at this time is calculated by the following expression (1) representing a color change in a three-dimensional colorimeter defined by L *, a *, b *, and a color filter with a high reliability can be manufactured as the color change value is small .
<Heat resistance>
The prepared color filter was heated in a heating oven at 230 캜 for 2 hours to compare and evaluate the color change before and after the evaluation. The formula to be used at this time is calculated by the equation (1) representing the color change in the three-dimensional colorimeter defined by L *, a *, b *, and as the color change value is smaller, Do.
<Hardness Measurement>
The manufactured color filter was measured for Martens Hardness (HM) using a microhardness tester.
Equipment and conditions were done as follows.
Equipment: Fischerscope H100C
Mode: Load-Unload
Loaing Speed: 0.15mN / sec
Total Loading Time: 8 sec
Loading Creep Time: 15 sec
Unloading Creep Time: 0 sec
Indenter: Vickers Indenter
?: Hardness value of not less than 250.0
?: Hardness value of 240.0 to 250.0
X: Hardness value less than 240.0
(? Eab *)
Referring to Table 1, when the colored photosensitive resin composition of the present invention is used, it is preferable that the photosensitive resin composition of the present invention is excellent in sensitivity and adhesion while maintaining the developing speed, and is free from peeling of the pattern during the developing process, and excellent in solvent resistance, heat resistance, The results were obtained.
Claims (6)
Wherein the colorant (A) comprises at least one pigment (a1) and at least one dye (a2)
Wherein the photopolymerizable compound (C) comprises a compound represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
R are, each independently, a hydrogen (-H) or a methyl group (-CH 3) and;
m and n are equal to each other and are 1 or 2;
(2)
In the above formula
R1 is the following formula 3,
R2 is C1-C8 alkyl, phenyl, substituted or unsubstituted phenyl, or substituted or unsubstituted benzyl group,
R3 is a diphenylsulfide group,
(3)
R4 is C1-C4 alkylene,
R5 is C3-C8 alkyl, C3-C8 cycloalkyl or C6-C8 aromatic hydrocarbon.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170096458A (en) * | 2016-02-16 | 2017-08-24 | 동우 화인켐 주식회사 | Photosensitive resin comopsition and photocurable pattern forming by the same |
-
2014
- 2014-03-19 KR KR1020140032144A patent/KR20150109106A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170096458A (en) * | 2016-02-16 | 2017-08-24 | 동우 화인켐 주식회사 | Photosensitive resin comopsition and photocurable pattern forming by the same |
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