KR20140015677A - Colored photosensitive resin composition and color filter - Google Patents
Colored photosensitive resin composition and color filter Download PDFInfo
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- KR20140015677A KR20140015677A KR1020120073482A KR20120073482A KR20140015677A KR 20140015677 A KR20140015677 A KR 20140015677A KR 1020120073482 A KR1020120073482 A KR 1020120073482A KR 20120073482 A KR20120073482 A KR 20120073482A KR 20140015677 A KR20140015677 A KR 20140015677A
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- resin composition
- photosensitive resin
- acrylate
- meth
- alkali
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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
- 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
- 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
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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
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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
Abstract
Description
The present invention relates to a colored photosensitive resin composition and a color filter.
A color filter can be embedded in a color imaging device of an image sensor, such as a complementary metal oxide semiconductor (CMOS) or a charge coupled device (CCD), and can be used to actually obtain a color image (PDP), a liquid crystal display (LCD), a field emission display (FEL), and a light emitting display (LED), and the application range thereof 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.
Such a color filter is manufactured by the method of forming a desired coloring pattern using the coloring photosensitive resin composition containing a coloring agent. Specifically, it is produced by forming a coating layer made of a colored photosensitive resin composition on a substrate, repeating a series of processes of forming a pattern on the formed coating layer, exposing and developing, heating and thermosetting.
As a colorant, a pigment is used. However, in this case, there is a problem that a desired luminance can not be obtained by a user. Recently, there has been an attempt to use a dye having high brightness and excellent heat resistance. The colorant is preferably used because it can realize all the excellent characteristics of the dye in the case of using only the dye, but the compatibility of the dye with the other components of the composition is worse than that of the pigment. Therefore, although a method of using a hybrid type coloring agent using both a pigment and a dye as coloring agents has been attempted, development characteristics are deteriorated. In the case of producing a color filter, the developing speed is slow and the sensitivity is insufficient. There is a problem that peeling of the formed pattern frequently occurs. Therefore, it is required to develop a colored photosensitive resin composition suitable for a lithographic process which can simultaneously satisfy the maintenance of a high luminance and the maintenance of good developing characteristics.
As the invention using a conventional colored photosensitive resin composition, Korean Patent Laid-Open No. 10-2003-0035869 discloses a dye-containing curable composition. However, in the case of the above conventional techniques, a developing speed is slowed, sensitivity and adhesion are problematic Peeling of the pattern may occur during the development process, resulting in poor processability, and low transmittance, chemical resistance and sensitivity.
Therefore, the colored photosensitive resin composition and the color filter according to the present invention provide a colored photosensitive resin composition which can obtain a color filter excellent in transmittance and excellent in reliability, has a high developing speed and is excellent in sensitivity and adhesion, It is an object of the present invention to provide a colored photosensitive resin composition and a color filter which are free from peeling, excellent in chemical resistance, and excellent in storage stability, and which do not decrease in sensitivity or increase in viscosity even when stored for a long time.
According to a feature of the present invention for achieving the above object, the present invention comprises a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, the alkali-soluble resin includes a repeating unit represented by the following formula (1) And, the colorant provides a color photosensitive resin composition comprising at least one selected from the group consisting of pigments and dyes.
[Formula 1]
(2)
In Chemical Formula 1, R 1 is represented by Chemical Formula 2, and in Chemical Formula 2, R 2 represents a residue or hydrogen including a carboxylic acid derived by an acid anhydride, and Y represents alkylene, ethylene oxide, and C1-C5. Any one selected from the group consisting of propylene oxide, R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms.
The present invention also provides a color filter comprising the colored photosensitive resin composition.
Therefore, the coloring photosensitive resin composition of this invention by the said subject solving means is excellent in a sensitivity and adhesiveness, can prevent the short circuit of a pattern in the image development process, and is excellent in the productivity of a color filter, and including the said coloring photosensitive resin composition It is possible to produce color filters having excellent contrast ratio, transmittance, chemical resistance and sensitivity.
Hereinafter, specific details of the color photosensitive resin composition and the color filter according to the present invention will be described.
The present invention includes a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the alkali-soluble resin includes a repeating unit represented by the following Chemical Formula 1, and the colorant is selected from the group consisting of pigments and dyes. It provides the coloring photosensitive resin composition containing one or more.
[Formula 1]
(2)
In Chemical Formula 1, R 1 is represented by Chemical Formula 2, and in Chemical Formula 2, R 2 represents a residue or hydrogen including a carboxylic acid derived by an acid anhydride, and Y represents alkylene, ethylene oxide, and C1-C5. Any one selected from the group consisting of propylene oxide, R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms.
The colorant comprises 5 to 60% by weight, 15 to 90% by weight of an alkali-soluble resin, and 5 to 45% by weight of a photopolymerizable compound, and the photopolymerization initiator is based on the total solids total weight of the colored photosensitive resin composition. And 0.1 to 40% by weight based on the content of the photopolymerizable compound, and the solvent preferably includes 60 to 90% by weight based on the total weight of the colored photosensitive resin composition.
The colorant preferably includes at least one member selected from the group consisting of a pigment and a dye. The pigment or dye is polymerized and crosslinked together with the alkali-soluble resin containing the compound of Formula 1 to determine the solvent resistance of the colored photosensitive resin composition It plays a role of improving.
Specifically, the pigment may be used an organic pigment or an inorganic pigment generally used in the art. In addition, the pigment may be used a variety of pigments used in printing inks, inkjet inks, and the like, specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, iso Indolin pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthhraquinoneyl pigments, anthrapyrimidine pigments, ananthronerone pigments, indanthrone pigments, pravantron pigments, It is preferably one or more selected from the group consisting of pyranthrone pigments and diketopyrrolopyrrole pigments, but is not limited thereto.
Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specifically, oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Or a composite metal oxide is preferable.
Examples of the organic pigment and the inorganic pigment include compounds classified as pigments in the color index (published by The society of Dyers and Colorists), and more specifically, pigments having the following color index (CI) numbers. Although it is preferable, it is not necessarily limited to these.
C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185
C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71
C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 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 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 Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Violet 23, C.I. Pigments selected from Pigment Blue 15: 3 and Pigment Blue 15: 6 can be preferably used.
It is preferable to use the pigment dispersion liquid which the said particle size disperse | distributed uniformly. As a method for uniformly dispersing the particle size of the pigment, there is a method of containing and dispersing the pigment dispersant. According to the above method, the pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained.
The content of the pigment is preferably included in 20 to 90% by weight, preferably 30 to 70% by weight relative to the total weight of solids of the pigment dispersion. When the content of the pigment satisfies the above-mentioned range, it is preferable because the viscosity is low, the storage stability is excellent and the dispersion efficiency is high, which is effective in increasing the contrast ratio.
The pigment dispersants include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine, and these may be used alone or in combination of two or more.
Moreover, the said pigment dispersant can also use the pigment dispersant of another resin type. The other resin type pigment dispersants include (partially) known pigment dispersants of known resin types, in particular polycarboxylic acid esters, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids represented by polyurethanes, polyacrylates. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or free ) Oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a carboxyl group with a poly (lower alkyleneimine); 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. As a commercial item of the said resin type dispersing agent, As a cationic resin dispersing agent, For example, brand names of BYK (Big) Chemi Corporation: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK- 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF brand name: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co., In addition to the acrylic dispersant described above, pigment dispersants of other resin types may be used alone or in combination of two or more thereof, or may be used in combination with acrylic dispersion.
The pigment dispersant is preferably included in 5 to 60% by weight, more preferably 15 to 50% by weight relative to the total weight of solids of the pigment. When the content of the dispersant satisfies the above-mentioned range, the viscosity is low, the fine particles of the pigment are possible, and gelation and the like can be prevented.
The dye can be used without limitation as long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility in an alkaline developer, heat resistance, solvent resistance, and the like.
Examples of the dye include acid dyes having an acidic group such as a sulfonic acid and a carboxylic acid, salts of an acidic dye and a nitrogen-containing compound, sulfonamides of an acidic dye and derivatives thereof, and azo, xanthate, phthalocyanine Based acid dyes and derivatives thereof.
Preferably, the dye may include a compound classified as a dye in the color index (Published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (color dyed yarn), but is not limited thereto.
Specific examples of the dye include C.I. As solvent dyes, C.I. Red dyes such as Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;
C.I. Blue dyes such as solvent blue 5, 35, 36, 37, 44, 59, 67, 70 and the like;
C.I. Violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49 and the like;
C.I. Yellow dyes such as solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;
C.I. Orange dyes such as solvent orange 2, 7, 11, 15, 26, 56
C.I. Green dyes such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and the like, and C.I. C.I. excellent solubility in organic solvents in solvent dyes. Solvent red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent blue 35, 36, 44, 45, 70; C.I. Solvent violet 13 is preferred, of which C.I. Solvent red 8, 122, 132 is more preferable.
Also, C.I. 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, Red dyes such as 346, 349, 382, 383, 394, 401, 412, 417, 418, 422 and 426;
CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 Yellow dyes such as, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251
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, etc.
Green dyes, such as C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. are mentioned.
CI Acid Red 92, which is excellent in solubility in organic solvents in acid dyes; C. I. Acid Blue 80, 90; C.I. Acid Violet 66 is preferred.
As a CI direct dye, CI direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184 Red dyes such as 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 and 250;
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;
Orange dyes such as C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
CI direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 Blue dyes such as, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc .;
Violet dyes such as C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
Green dyes, such as C.I. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. are mentioned.
Also, C.I. As a modanto dye, yellow dyes, such as C.I. modanto yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
CI 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 CI Modatto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43,
The content of the dye in the colorant is preferably contained 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, particularly preferably 1 to 50% by weight relative to the solid content of the colorant. When the content of the dye in the colorant satisfies the above-described range, it is possible to prevent the problem of lowering the reliability of the dye eluted by the organic solvent after the pattern formation, it is preferable because the sensitivity is excellent.
The colorant is preferably contained in 5 to 60% by weight, more preferably 10 to 45% by weight relative to the solid content of the colored photosensitive resin composition. When the colorant satisfies the above-mentioned range, even when a thin film is formed, the color density of the pixel is sufficient, and the omission of the non-pixel portion during development does not decrease, so that residues can be suppressed.
It is preferable that the said alkali-soluble resin contains the repeating unit of following General formula (1) as an essential component.
[Formula 1]
(2)
In Chemical Formula 1, R 1 is represented by Chemical Formula 2, and in Chemical Formula 2, R 2 represents a residue or hydrogen including a carboxylic acid derived by an acid anhydride, and Y represents alkylene, ethylene oxide, and C1-C5. Any one selected from the group consisting of propylene oxide, R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms.
The unsaturated double bond contained in the repeating units represented by Formulas 1 and 2 serves to impart photocurability and thermosetting to the alkali-soluble resin.
In order to ensure compatibility and storage stability of the coloring photosensitive resin composition, the acid value of the alkali-soluble resin is preferably 30 to 150 mgKOH / g. When the acid value of the alkali-soluble resin satisfies the above-mentioned range, the colored photosensitive resin composition can secure a sufficient developing speed, and the adhesion with the substrate is increased to suppress the occurrence of short circuit of the pattern, and improve compatibility and storage stability. do.
The acid anhydride is a reaction material for inducing carboxylic acid in Chemical Formula 2, succinic anhydride, glutaric anhydride, 3-methyl glutaric anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, butyl succinic anhydride , 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride, 1,1-cyclopentanediacetic acid anhydride, (2-methyl-2 -Propenyl) succinic anhydride, 3,3-dimethylglutaric anhydride, 2,2-dimethylglutaric anhydride, 1,1-cyclohexanediacetic anhydride, 2-buten-1-ylsuccinic anhydride, 3-methyl 4-cyclohexene-1,2-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, n-octyl succinic anhydride, allyl succinic anhydride, bicyclo [2.2.2] octa-5-ene-2,3-dicarboxylic acid anhydride, phthalic anhydride, 4-methylphthalic anhydride, 2,3-naphthalenedicarboxyl Mountain Anhydride, 1,2-naphthalenedicarboxylic acid anhydride, 3-methylphthalic anhydride, diphenic anhydride, 1-cyclohexene-1,2-dicarboxylic acid anhydride, 5,6-dihydro-1,4-dichine- It is preferably at least one acid anhydride selected from the group consisting of 2,3-dicarboxylic acid anhydride, 2,3-dimethylmaleic anhydride, maleic anhydride, 4-tert-butylphthalic anhydride and citraconic anhydride, It is not limited to this.
The alkali-soluble resin may include a copolymer of a compound including a repeating unit of Formula 1 and an unsaturated bond, and the compound including the unsaturated bond is not limited as long as the compound has a double bond.
Preferably, the compound containing an unsaturated bond is a substituted alkyl ester compound of an unsaturated carboxylic acid, an unsaturated carboxylic acid ester compound including an alicyclic substituent, a glycol monosaturated carboxylic acid ester compound, a substituent having an aromatic ring. Unsaturated carboxylic acid esters, aromatic vinyl compounds, carboxylic acid vinyl esters, vinyl cyanide compounds, maleimide compounds, and the like, and specifically, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth). Acrylate, aminoethyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylic Elate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycle Heptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, pentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylic Latene, norbornyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, methylglycid Dill (meth) acrylate, oligoethylene glycol monoalkyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, vinyl acetate, vinyl propionate, ( It is preferably at least one compound selected from the group consisting of meta) acrylonitrile, α-chloroacrylonitrile, N-cyclohexylmaleimide and N-phenylmaleimide.
The photopolymerizable compound is a compound capable of polymerizing under the action of the photopolymerization initiator described below, and may be a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer, and preferably a bifunctional or multifunctional monomer may be used.
Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N- But are not limited thereto.
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) , Bis (acryloyloxyethyl) ether of bisphenol A or 3-methylpentanediol di (meth) acrylate, but are not limited thereto.
Specific examples of the polyfunctional monomer include trimethylol propane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, and pentaerythritol tree. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) ) Acrylate or dipentaerythritol hexa (meth) acrylate, and the like, but is not limited thereto.
The repeating unit represented by the formula (1) is preferably contained in 5 to 80 mol%, more preferably 20 to 70 mol% based on the total number of moles of the alkali-soluble resin. When the above-mentioned range is satisfied, the balance of developability, solubility, and heat resistance is good, and a preferable alkali-soluble resin can be obtained.
The repeating unit of Chemical Formula 1 is preferably prepared by reacting the following Chemical Formulas 3 and 4 and reacting the acid anhydride.
(3)
[Chemical Formula 4]
In Formula 4, Z is alkylene, ethylene oxide or propylene oxide having 1 to 5 carbon atoms, and R 4 is an alkyl group or hydrogen having 1 to 6 carbon atoms.
The compound of Formula 3 including the acid functional group may be prepared by any one of various polymerization methods known in the art, such as radical polymerization, cationic polymerization, anionic polymerization, and condensation polymerization. It is preferable to use radical polymerization from the viewpoint of ease of use and economy.
Specifically, the monomer may be prepared by mixing the monomer with a polymerization solvent, heating to an appropriate temperature, and then removing oxygen through nitrogen purging. In addition, preferably, a compound of Formula 3 may be prepared by adding a radical polymerization initiator and a chain transfer agent and maintaining the polymerization temperature, if necessary. In the above method, the polymerization temperature and the polymerization time can be determined in consideration of the half life period of the polymerization initiator to be used depending on the temperature.
For example, since the half life of 2,2'-azobisisobutyronitrile (AIBN) at 70 ° C is 4.8 hours, the polymerization time when using this is preferably 6 hours or more. The polymerization temperature is preferably between 50 ° C and 150 ° C, and the polymerization time is preferably 30 minutes to 48 hours, but is not limited thereto.
As the radical polymerization initiator, those known in the art may be used, and specific examples thereof include 2,2'-azobisisobutyronitrile (AIBN) and 2,2'-azobis- (2,4-dimethylvalle. Ronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1,1'- Bis- (bis-t-butylperoxy) cyclohexane and the like are preferred, but not limited thereto.
The chain transfer agent is used to control the weight average molecular weight, and specific examples thereof include n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid. , 3-mercaptopropionic acid, alpha-methylstyrene dimer, and the like, but are not limited thereto, and those known in the art may be used.
The monomer used for preparing the copolymer is preferably an aromatic or aliphatic vinyl monomer copolymerizable, and specifically, styrene, chlorostyrene, α-methyl styrene, vinyltoluene, methyl (meth) acrylate, ethyl (meth) Acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate , Isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydroperpril (meth) acrylate, hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylic Ethylene, ethylhexyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, Methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypoly Propylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate It is preferably at least one selected from the group consisting of heptadecafluorodecyl (meth) acrylate and tribromophenyl (meth) acrylate.
The compound of Formula 4 is an ethylenically unsaturated compound including an epoxy group, and serves to introduce a photoreactive group into the copolymer.
The compound of Formula 4 is specifically glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-norbornene-2-carboxylate (endo, exo mixture) and It is preferably one or more selected from the group consisting of 5-norbornene-2-methyl-2-carboxylate (endo, exo mixture), but is not limited thereto.
When the reactive resin solution obtained by the reaction of the resin of Formula 3 and the compound of Formula 4 is added to a flask with a stirrer, glycidyl methacrylate and cyclohexene oxide are added and then the epoxy group is removed. It is preferable to react to.
It is preferable that the weight average molecular weight of polystyrene conversion of the alkali-soluble resin containing the repeating unit of the said Formula (1) exists in the range of 3,000-100,000, and it is more preferable that it exists in the range of 5,000-50,000. When the weight average molecular weight of the said alkali-soluble resin exists in the said range, film | membrane decrease hardly arises at the time of image development, and since the missing property of a non-pixel part at the time of image development tends to be favorable, it is preferable.
The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the alkali-soluble resin is preferably 1.0 to 6.0, more preferably 1.3 to 4.0. When the molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) is 1.5 to 6.0, development is preferable.
The photopolymerizable compound is a compound capable of polymerizing under the action of the photopolymerization initiator described below, and may be a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer, and preferably a bifunctional or multifunctional monomer may be used.
Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N- But are not limited thereto.
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) , Bis (acryloyloxyethyl) ether of bisphenol A or 3-methylpentanediol di (meth) acrylate, but are not limited thereto.
Specific examples of the polyfunctional monomer include trimethylol propane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, and pentaerythritol tree. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) ) Acrylate or dipentaerythritol hexa (meth) acrylate, and the like, but is not limited thereto.
It is preferable that 5 to 45 weight% of said photopolymerizable compound is contained with respect to the total solid of a coloring photosensitive resin composition, More preferably, it is 7 to 45 weight%. When the content of the photopolymerizable compound satisfies the above-mentioned range, the intensity or smoothness of the pixel portion becomes good, which is preferable.
The photopolymerization initiator can be used without particular limitation as long as it can polymerize the photopolymerizable compound. Particularly, from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and cost, the photopolymerization initiator is preferably used in combination with an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, It is preferable to use at least one compound selected from the group consisting of compounds.
The acetophenone compound may be diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy ) Phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, etc. are mentioned.
As said benzophenone type compound, benzophenone, methyl 0- benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3,3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone and at least one selected from the group consisting of 2,4,6-trimethylbenzophenone, but is not limited thereto.
The triazine-based compound is 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4 -Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloro To methyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) Tenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6 -[2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine may be one or more selected from the group consisting of, but is not limited thereto.
The biimidazole compound is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl)- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2, 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4', At least one selected from the group consisting of 5,5'-tetraphenyl-1,2'-biimidazole and an imidazole compound in which a phenyl group at the 4,4 ', 5,5' position is substituted by a carboalkoxy group 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl ) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'- It is more preferable that it is biimidazole.
The oxime compound is preferably o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, but is not limited thereto.
The thioxanthone compound is selected from the group consisting of 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone and 1-chloro-4-propoxy thioxanthone. It may be one or more, but is not limited thereto.
In addition, the photopolymerization initiator may further include a photopolymerization initiation aid in order to improve the sensitivity of the colored photosensitive resin composition of the present invention.
The photopolymerization initiation adjuvant is preferably 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.
The amine compound is preferably an aromatic amine compound, and specifically, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, or 4-dimethylaminobenzoic acid. Isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), 4 , 4'-bis (diethylamino) benzophenone and the like.
The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically, 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, and 1,3,5-tris (3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropanetris (3-mergaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl Rate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and the like. .
The photopolymerization initiator may be included in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the content of the alkali-soluble resin and the photopolymerizable compound. When the content of the photopolymerization initiator satisfies the above-mentioned range, since the colored photosensitive resin composition is highly sensitive and the exposure time is shortened, the productivity is improved and high resolution is preferable. 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 addition, it is preferable that the photopolymerization initiator further comprises a photopolymerization initiation aid, wherein the photopolymerization initiation agent is preferably included in an amount of 0.1 to 40% by weight, more preferably, based on the content of the alkali-soluble resin and the photopolymerizable compound. Is preferably included 1 to 30% by weight. When the content of the photopolymerization initiation assistant satisfies the above-mentioned range, the sensitivity of the photosensitive resin composition is higher, and the productivity of the color filter formed using the composition is improved.
If the solvent is effective to dissolve the other components included in the colored photosensitive resin composition, it can be used without particular limitation to the solvent used in ordinary colored photosensitive resin composition, ethers, aromatic hydrocarbons, ketones, alcohols, esters And it is preferably at least one selected from the group consisting of amides.
Specifically, the solvent is ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate, methoxy pentyl acetate Alkylene glycol alkyl ether acetates such as these; 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, and cyclic esters such as γ-butyrolactone.
The solvent is preferably an organic solvent having a boiling point of 100 ℃ to 200 ℃ in terms of applicability and drying properties, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalac Tate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.
The solvent is preferably included in 60 to 90% by weight, more preferably 70 to 85% by weight based on the total weight of the colored photosensitive resin composition. When the content of the solvent satisfies the above-mentioned range, the coating property is improved when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, etc. To provide.
It is preferable to further include an additive in the said colored photosensitive resin composition, The said additive contains a polymeric compound containing hardenable resin or a thermoplastic resin, a hardening | curing agent, surfactant, an adhesion promoter, antioxidant, a ultraviolet absorber, anti-agglomeration agent, etc.
The polymer compound containing the curable resin or the thermoplastic resin may be curable resin such as epoxy resin or maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane or the like. Thermoplastic resins, etc., but is not limited thereto.
The curing agent is used to increase the core hardening and mechanical strength, and there are epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds and the like, but is not limited thereto.
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, noblock type epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin , Glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins, aliphatic, cycloaliphatic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, isoprene ( Co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like.
Specific examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane 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. Examples of the curing aid compound include polyhydric carboxylic acids, polyhydric carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. As a specific example of the said epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) (New Nippon Ewha Co., Ltd.) etc. are mentioned. The hardeners illustrated above can be used individually or in mixture of 2 or more types.
The surfactant may be used to further improve the film formability 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.
The adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane , But is preferably at least one selected from the group consisting of 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane, but is not limited thereto.
The antioxidants include, but are not limited to, 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.
The ultraviolet absorbers include, but are not limited to, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone, and the like. Examples of the anti-agglomeration agent include sodium polyacrylate, but are not limited thereto.
The present invention provides a color filter comprising the colored photosensitive resin composition.
The color filter according to the present invention comprises a step of applying the solution of the colored photosensitive resin composition, applying the patterned exposure to a dry coating film obtained by pre-baking, and then developing the color filter, thereby obtaining a color of the coloring agent A pixel or a black matrix corresponding to the black matrix is obtained. In addition, the color filter can be obtained by repeating this process for the number of colors required for the color filter.
Since the configuration and manufacturing method of the color filter are well known in the art, it is possible to manufacture a color filter using the same.
Hereinafter, the present invention will be described in detail with reference to the following examples. However, the present invention is not limited to the following examples.
< Manufacturing example >
1. Preparation of Pigment Dispersion
C.I. Pigment Blue 15: 6 12.0g, 4.0 g of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 44 g of propylene glycol methyl ether acetate and 40 g of propylene glycol methyl ether as a solvent were mixed and dispersed for 12 hours using a pigment A dispersion was prepared.
< Example 1>
1. Preparation of Alkali Soluble Resin
120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of 2,2'-azobisisobutyronitrile, 4-vinyl in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. 35.0 g of benzoic acid, 5.9 g of 4-methylstyrene, 5.0 g of benzyl methacrylate, and 3 g of n-dodecyl mercapto were added thereto, followed by nitrogen substitution.
After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. Subsequently, the temperature of the reaction solution was lowered to room temperature, and the flask atmosphere was replaced with nitrogen from air. Then, 0.2 g of triethylamine, 0.1 g of 4-methoxy phenol and 34.1 g of glycidyl methacrylate were added thereto, and the mixture was heated at 100 ° C. for 6 hours. Reacted. Thereafter, the temperature of the reaction solution was decreased to room temperature, and 20.0 g of cis-4-cyclohexene-1,2-dicarboxylic acid anhydride was added thereto and reacted at 80 ° C. for 12 hours.
The solid acid value of the alkali-soluble resin thus synthesized was 73.5 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 13750.
2. Preparation of colored photosensitive resin composition
22.5 g of the pigment dispersion prepared in Preparation Example 1, C.I. 0.3 g of solvent blue 44 (Orient Chemical Co., Ltd., VALIFAST BLUE 2620), 16.5 g of said alkali-soluble resin, dipenta erythritol hexa (meth) acrylate (Nippon Kayaku, KAYARAD DPHA) 5.0 g, alpha-amino aceto 0.3 g of phenone (BASF, Irgacure 907), 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzyloxime) (BASF, Irgacure OXE01) 0.7 g, propylene glycol monomethyl 20.5 g of ether acetate and 34.0 g of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.
< Example 2>
1. Preparation of Alkali Soluble Resin
120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of 2,2'-azobisisobutyronitrile, 4-vinyl in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. 20.0 g of benzoic acid, 28.5 g of 4-methylstyrene, 10 g of benzyl methacrylate, 10 g of methyl methacrylate, and 3 g of n-dodecyl mercapto were added and nitrogen-substituted.
After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. Subsequently, the reaction solution was cooled to room temperature, and the flask atmosphere was replaced with nitrogen from air, followed by 0.2 g of triethylamine, 0.1 g of 4-methoxy phenol, and 18.5 g of glycidyl methacrylate, followed by 6 hours at 100 ° C. Reacted. Thereafter, the temperature of the reaction solution was lowered to room temperature, 13.0 g of succinic anhydride was added thereto, and the reaction was performed at 80 ° C. for 12 hours.
The solid acid value of the alkali-soluble resin thus synthesized was 77.5 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 15301.
2. Preparation of colored photosensitive resin composition
It manufactured similarly to Example 1, and prepared the coloring photosensitive resin composition.
< Example 3 >
1. Preparation of Alkali Soluble Resin
120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of 2,2'-azobisisobutyronitrile, 4-vinyl in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. 27.0 g of benzoic acid, 12.4 g of 4-methylstyrene, 10 g of benzyl methacrylate, 10 g of methyl methacrylate, and 3 g of n-dodecyl mercapto were added and nitrogen-substituted.
After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. Subsequently, the temperature of the reaction solution was lowered to room temperature, and the flask atmosphere was replaced with nitrogen from air. Then, 0.2 g of triethylamine, 0.1 g of 4-methoxy phenol, 25.6 g of glycidyl methacrylate were added thereto, and the mixture was heated at 100 ° C. for 6 hours. Reacted. Thereafter, the reaction solution was cooled to room temperature, 15.0 g of succinic anhydride was added thereto, and the reaction mixture was reacted at 80 ° C. for 12 hours.
The solid acid value of the alkali-soluble resin thus synthesized was 87.5 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 14250.
2. Preparation of colored photosensitive resin composition
It manufactured similarly to Example 1, and prepared the coloring photosensitive resin composition.
< Comparative Example 1>
1. Preparation of Alkali Soluble Resin
120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of 2,2'-azobisisobutyronitrile, methacrylic acid 13.0 in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube g, 67.0 g of 4-methylstyrene, 10 g of benzyl methacrylate, 10 g of methyl methacrylate, and 3 g of n-dodecyl mercapto were added and nitrogen-substituted.
After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. The solid acid value of the alkali-soluble resin thus synthesized was 81.6 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 16110.
2. Preparation of colored photosensitive resin composition
It manufactured similarly to Example 1, and prepared the coloring photosensitive resin composition.
< Comparative Example 2>
1. Preparation of Alkali Soluble Resin
120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of 2,2'-azobisisobutyronitrile, methacrylic acid 5.0 in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. g, 55.0 g of 4-methylstyrene, 20 g of benzyl methacrylate, 20 g of methyl methacrylate, and 3 g of n-dodecyl mercapto were added thereto, followed by nitrogen substitution.
After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. The solid acid value of the alkali-soluble resin thus synthesized was 17.4 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 17370.
2. Preparation of colored photosensitive resin composition
It manufactured similarly to Example 1, and prepared the coloring photosensitive resin composition.
< Comparative Example 3>
1. Preparation of Alkali Soluble Resin
120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of 2,2'-azobisisobutyronitrile, methacrylic acid 60.0 in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. g, 4-methylstyrene 10.0 g, benzyl methacrylate 10 g, methyl methacrylate 10 parts n-dodecyl mercapto 3g were added, and it substituted by nitrogen.
After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. The solid acid value of the alkali-soluble resin thus synthesized was 172.3 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 11874.
2. Preparation of colored photosensitive resin composition
It manufactured similarly to Example 1, and prepared the coloring photosensitive resin composition.
< Experimental Example >
1. Manufacture of color filters
Color filters were prepared using the colored photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 3.
Specifically, each of the colored photosensitive resin composition was coated on a 2-inch angle glass substrate (Corning Corporation, EAGLE XG) by spin coating, then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film.
Subsequently, a test photomask having a pattern for changing the transmittance stepwise in a range of 1 to 100% and a line / space pattern of 1 μm to 50 μm was placed on the thin film and the distance from the test photomask was 100 μm. Was investigated. 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 UV-irradiated thin film was developed by soaking in a KOH aqueous solution developing solution of pH 10.5 for 2 minutes. The glass plate coated with the thin film was washed with distilled water, blown with nitrogen gas, dried, and heated in a heating oven at 200 ° C for 25 minutes to prepare a color filter. The film thickness of the manufactured color filter was 2.0 μm.
2. Evaluation of adhesion
When the generated pattern was evaluated through an optical microscope, the degree of tearing on the pattern was evaluated as no pattern tearing (○), 1 to 3 pattern tearing (△), and 4 or more pattern tearing (×). It is shown in Table 1 below.
3. Evaluation of developing speed
The time taken for the non-exposed part to completely dissolve in the developing solution at the time of image development was measured.
4. Chemical resistance measurement
The prepared color filter was immersed in an NMP solution at room temperature for 30 minutes, washed with ultrapure water and dried for 2 minutes on a hot plate heated to 120 ° C, and the chromaticity before and after immersion was measured. At this time, the chromaticity change rate (ΔE * ab) is 3.0 or less (○), 3.0 or more (X).
5. Sensitivity Measurement
The minimum exposure amount whose (pre-development film thickness / post-development film thickness x 100) becomes 90% or more is expressed by the sensitivity.
6. Contrast Ratio Measurement
Contrast ratio was measured using the color filter manufactured similarly in the said color filter manufacture except having not used the test photomask.
In the case of contrast ratio, the substrate of the color filter is sandwiched between two deflection plates, and the maximum and minimum values of the light intensity transmitted by rotating the front deflection plate while illuminating the fluorescent lamp (wavelength 380 to 780 nm) from the rear side are CS. The contrast ratio was calculated using a -2000 luminance meter (KONICA MINOLTA) and the maximum value divided by the minimum value. The transmittance was measured using a colorimeter (Olympus, OSP-200).
As shown in Table 1, in the case of the color filter manufactured using the colored photosensitive resin compositions of Examples 1 to 3, the development speed, adhesion, chemical resistance and sensitivity of the colored photosensitive resin compositions of Comparative Examples 1 to 3 were used. It can be seen that the improvement compared to the case of the manufactured color filter.
Claims (5)
The alkali-soluble resin includes a repeating unit represented by the following formula (1),
The coloring photosensitive resin composition comprising at least one colorant selected from the group consisting of pigments and dyes.
[Chemical Formula 1]
(2)
In Formula 1, R 1 is represented by Formula 2, and in Formula 2, R 2 represents a residue or hydrogen including a carboxylic acid derived by an acid anhydride, and Y represents alkylene, ethylene oxide, and C 1-5 Any one selected from the group consisting of propylene oxide, R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020120073482A KR20140015677A (en) | 2012-07-05 | 2012-07-05 | Colored photosensitive resin composition and color filter |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020120073482A KR20140015677A (en) | 2012-07-05 | 2012-07-05 | Colored photosensitive resin composition and color filter |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150109099A (en) * | 2014-03-19 | 2015-10-01 | 동우 화인켐 주식회사 | A colored photosensitive resin composition for color filter, color filter and liquid crystal display device having the same |
| KR20160109609A (en) * | 2015-03-12 | 2016-09-21 | 동우 화인켐 주식회사 | Colored photosensitive resin composition |
-
2012
- 2012-07-05 KR KR1020120073482A patent/KR20140015677A/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150109099A (en) * | 2014-03-19 | 2015-10-01 | 동우 화인켐 주식회사 | A colored photosensitive resin composition for color filter, color filter and liquid crystal display device having the same |
| KR20160109609A (en) * | 2015-03-12 | 2016-09-21 | 동우 화인켐 주식회사 | Colored photosensitive resin composition |
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