KR102028580B1 - Colored photosensitive resin composition for forming column spacer - Google Patents
Colored photosensitive resin composition for forming column spacer Download PDFInfo
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- KR102028580B1 KR102028580B1 KR1020130103607A KR20130103607A KR102028580B1 KR 102028580 B1 KR102028580 B1 KR 102028580B1 KR 1020130103607 A KR1020130103607 A KR 1020130103607A KR 20130103607 A KR20130103607 A KR 20130103607A KR 102028580 B1 KR102028580 B1 KR 102028580B1
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
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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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Abstract
The present invention relates to a colored photosensitive resin composition, and more particularly, includes (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photoinitiator, and (E) a solvent. The coloring agent (A) includes a mixture of pigment blue 16 and pigment blue 60 and at least one pigment and a black pigment, and relates to a colored photosensitive resin composition which is free of metal components and excellent in color characteristics and near infrared transmittance.
Description
The present invention relates to a colored photosensitive resin composition, and more particularly, to a colored photosensitive resin composition in which a metal component is not eluted and excellent in color characteristics and near-infrared transmittance.
Recently, liquid crystal displays have been spotlighted as next generation advanced display devices having low power consumption, good portability, high technology value, and high added value.
Among the liquid crystal display devices, an active matrix liquid crystal display device having a thin film transistor, which is a switching element that can control voltage on / off for each pixel, has the best resolution and video performance. It is attracting attention.
In general, an LCD device forms an array substrate and a color filter substrate through an array substrate manufacturing process for forming a thin film transistor and a pixel electrode, and a color filter substrate manufacturing process for forming a color filter and a common electrode, respectively. It completes through the liquid crystal cell process through a liquid crystal between them.
Column spacers are formed in the liquid crystal cell to maintain a constant cell gap. The column spacer has limitations in thickness change (dimension stability) with respect to external pressure generated in the cell process, chemical resistance to etchant, strip liquid, and the like, and reactivity with liquid crystal molecules.
That is, when external pressure is applied in bonding of the substrate, etc., dimensional stability that can keep the cell gap constant without large change in the thickness is required. Since the column spacer is in contact with the liquid crystal molecules of the liquid crystal layer, non-reactivity with the liquid crystal molecules is required such that the column spacer does not react with the liquid crystal molecules or the impurities of the column spacer are not eluted into the liquid crystal layer.
Conventionally, carbon black has been used as a coloring agent in the coloring photosensitive resin composition for forming a column spacer.
However, carbon black has the disadvantage of low electrical resistance. Therefore, although it is applied as a high-resistance material through the surface treatment of carbon, in the case of carbon black, when it is made of a colored photosensitive resin composition, it is difficult to control the improvement of the dielectric constant due to the properties of the carbon material, and it is near infrared (Near-IR). The transmittance characteristic is very bad.
Therefore, a method of using an organic pigment in combination has been developed, and Pigment Blue 15: 6 is used as a representative organic pigment. In the case of Pigment Blue 15: 6, however, the metal is eluted, which causes a problem in driving the display.
Korean Patent Publication No. 2010-66197 discloses a black photosensitive resin composition, and a light shielding layer and a column spacer using the same.
An object of this invention is to provide the coloring photosensitive resin composition containing the organic pigment which was excellent in reliability.
Moreover, another object of this invention is to provide the coloring photosensitive resin composition which is excellent in the spectrum of a visible light region, and excellent in electrical insulation and near-infrared transmittance.
Another object of the present invention is to provide a color filter, a black matrix, and a column spacer using a colored photosensitive resin composition.
1. (A) a coloring agent, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photoinitiator, and (E) solvent, Comprising: (A) coloring agent pigment blue 16 and pigment blue 60 The coloring photosensitive resin composition containing the mixture of at least 1 sort (s) and a black pigment.
2. In the above 1, the mixed weight ratio of pigment blue 16 and pigment blue 60 and at least one pigment black is 1: 0.15 to 1: 3, the colored photosensitive resin composition.
3. In the above 1, when Pigment Blue 16 and Pigment Blue 60 are used together, the mixing weight ratio is 1: 0.15 to 1: 3, the colored photosensitive resin composition.
4. according to the above 1, wherein the black pigment is carbon black, coloring photosensitive resin composition.
5. Electronic device manufactured from the coloring photosensitive resin composition of the above 1 to 4.
6. The electronic device according to the above 5, which is at least one selected from the group consisting of color filters, black matrices and column spacers.
7. Image display device including the electronic device of the above five.
The coloring photosensitive resin composition of this invention does not elute the metal component using pigment blue 16 and 60 as a coloring agent. Therefore, the reliability of the display device is not deteriorated even if it is made of the column spacer inside the liquid crystal cell.
Moreover, the coloring photosensitive resin composition of this invention is excellent in color characteristic and near-infrared transmittance.
This invention contains (A) coloring agent, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photoinitiator, and (E) solvent, The said (A) coloring agent is pigment blue 16 and a pigment By containing the mixture of at least 1 sort (s) of blue 60 and a black pigment, it is related with the coloring photosensitive resin composition in which a metal component is not eluted and excellent in color characteristics and near-infrared transmittance.
<Coloring Photosensitive Resin Composition>
The light shielding layer for improving contrast ratio and color development effect, which is used in color filters and the like, is made of a colored photosensitive resin composition.
Recently, such a colored photosensitive resin composition is also used to manufacture a cell gap maintaining spacer. In addition, the near-infrared transmittance and color characteristics must be excellent, and the column spacer is used as a cell gap maintaining pattern in the liquid crystal layer, so that a metal component or a colorant component elutes. There needs to be no.
The colored photosensitive resin composition of the present invention can be usefully used as a column spacer because it can maintain excellent near-infrared transmittance and color characteristics without eluting a metal component or a colorant component, including a colorant of a specific component.
Hereinafter, the present invention will be described in detail.
Colorant (A)
The colorant according to the present invention is a C.I. Pigment Blue 16 and C.I. At least one of Pigment Blue 60 and a black pigment are included as essential components.
The composition of the present invention can prevent the dissolution of the colorant component and the metal component by including the mixed pigment as a colorant, it can exhibit excellent color characteristics and near infrared transmittance.
In the present invention, C.I. Pigment Blue 16 and C.I. It is preferable that the mixing weight ratio of at least 1 sort (s) of pigment blue 60 and a black pigment is 1: 0.15-1: 3. Within the above range, the near infrared transmittance is excellent and the color characteristics are excellent.
In the present invention, C.I. Pigment Blue 16 and C.I. If Pigment Blue 60 is used together, C.I. Pigment Blue 16 and C.I. It is preferable that the mixing weight ratio of pigment blue 60 is 1: 0.15-1: 3. Within this range, there is an advantage in that the color characteristics of the visible light region are excellent.
The black pigment usable in the present invention may be used without particular limitation to the black pigment used in the art, for example, CI pigment black 1 and 7, carbon black, etc. may be used alone or in combination of two or more, respectively. Preferably carbon black can be used.
The colorant according to the present invention may further include pigments and dyes used in the art in addition to the aforementioned pigments without departing from the object of the present invention.
The colorant according to the present invention may be included in an amount of 3 to 50% by weight based on the total weight of solids in the colored photosensitive resin composition. When a coloring agent is contained in the said range, color reproducibility and near-infrared transmittance are favorable.
(a1) pigment
Pigment (a1) contains an organic pigment and an inorganic pigment.
As the organic pigment, various pigments used in printing ink, inkjet ink, and the like may be used. Specifically, phthalocyanine (aqueous azo pigment, insoluble azo pigment), phthalocyanine pigment, quinacridone pigment, isoin Dolanone pigments, isoindolin pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthhraquinonyl pigments, anthrapyrimidine pigments, ananthrone pigments, indanthrone pigments, Pravantron pigments, pyranthrone pigments or diketopyrrolopyrrole pigments and the like.
Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specifically, oxides or composites of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony Metal oxides; and the like.
In particular, the organic pigments and inorganic pigments include compounds that are specifically classified as pigments in the color index (published by The society of Dyers and Colourists), and more specifically, the following color index (CI) numbers Although a pigment is mentioned, It is not necessarily limited to these.
As the pigment used in the pigment dispersion composition according to the present invention, an organic pigment or an inorganic pigment generally used in the art may be used, and these may be used alone or in combination of two or more kinds.
If necessary, the pigment may be a resin treatment, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the surface of the pigment with a high molecular compound or the like, an atomization treatment by a sulfate atomization method or the like to remove impurities. The washing treatment with an organic solvent or water, the removal of ionic impurities by an ion exchange method, or the like may be performed.
Specific examples of the pigment,
C.I. Pigment Yellow 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 21, 28, 64 and 76;
C.I. Pigment green 7, 10, 15, 25, 36, 47 and 58;
CI Pigment Brown 28; Etc. can be mentioned.
C.I. exemplified above. Among pigment pigments, C.I. Pigment Red series and C.I. Pigments selected from pigment violet series can be preferably used.
It is preferable to use the pigment dispersion liquid which the said particle size disperse | distributed uniformly. As an example of the method for uniformly dispersing the particle size of the pigment, a method of containing and dispersing the pigment dispersant may be used. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.
In the coloring photosensitive resin composition of this invention, the said (a1) pigment can be contained in the form of a pigment dispersion composition.
The pigment dispersion composition includes (a1) a pigment, (a2) a dispersant, (a3) a dispersing aid, and (a4) a dispersing solvent, and (a5) a dispersing resin may be added to facilitate storage stability and dispersion.
In addition, the pigment (a1) may be included in the range of 20 to 90% by weight, preferably 30 to 70% by weight based on the total weight of the solid content in the pigment dispersion composition. If the content of the pigment is not included in the above range is high viscosity, poor storage stability, low dispersion efficiency adversely affects the contrast ratio.
(a2) dispersant
The dispersant is added to maintain the stability of the pigment and deagglomeration can be used without limitation to those commonly used in the art. The dispersant preferably includes an acrylate dispersant (hereinafter referred to as an acrylate dispersant) including butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Commercially available products of the acrylate-based dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150, and the like. Each of the acrylate-based dispersants may be used alone or in combination of two or more thereof. Can be.
The dispersant according to the present invention may use a pigment dispersant of another resin type in addition to the acrylate-based dispersant. The other resin type pigment dispersants include known resin type pigment dispersants, in particular polycarboxylic acid esters represented by polyurethanes, polyacrylates, unsaturated polyamides, polycarboxylic acids, amine salts of polycarboxylic acids, Ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of polycarboxylic acids substituted with hydroxyl groups and modified products thereof, free carboxyl groups Amides or salts thereof formed by the reaction of polyesters with poly (lower alkyleneimines), (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate ester copolymers, styrene-maleic acid copolymers Water-soluble resins or water-soluble polymer compounds such as polymers, polyvinyl alcohol, polyvinyl pyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide and phosphate esters.
Commercially available products of the resin type pigment dispersant include cationic resin dispersants, for example, the trade names of BYK (BIC) Chemisa: 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; Product name of BASF Corporation: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Kawaken Fine Chemical's trade names: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Trade names: AJISPUR PB-821, Azisper PB-822, Azisper PB-823; The brand names of Kyoeisha Chemical Co., Ltd. are: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORON DOPA-33, FLORON DOPA-44, and the like.
The dispersant is included in an amount of 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the pigment in the colorant. If the dispersant exceeds 60 parts by weight, the viscosity may be increased. If the dispersant is less than 5 parts by weight, it may be difficult to atomize the pigment, or may cause problems such as gelation after dispersion.
In addition to the dispersant described above, surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine based may be used as the dispersant, and these may be used alone or in combination of two or more.
Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and polyethyleneimines. And KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Mega Pack (MEGAFAC) (manufactured by Dainippon Ink & Chemicals Co., Ltd.), Florard (manufactured by Sumitomo 3M Inc.), Asahi guard, Suflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE ) (Manufactured by Geneva Co., Ltd.), EFKA (manufactured by EFKA Chemicals Co., Ltd.), PB 821 (manufactured by Ajinomoto Co., Ltd.), and the like.
(a3) Dispersion Aids
Dispersion aid refers to a formulation that serves to prevent reagglomeration by dispersing the pigment into fine particles. The dispersing aid is effective in forming a colored layer having a high contrast ratio and excellent transmittance.
Dispersion aids usable in the present invention include, for example, 1,8-diamino-4,5-dihydroxyanthraquinone, 1,5-bis {[2- (diethylamino) ethyl] amino} anthra- 9,10-quinone, 1,8-bis (benzamido) anthraquinone, 1,4-bis {[2- (4-hydroxyphenyl) ethyl] amino} anthra-9,10-quinone, 1,4 -Bis {[2- (dimethylamino) ethyl] amino} -5,8-dihydroxyanthra-9,10-quinone, 1,8-dihydroxy-4- [4- (2-hydroxyethyl ) Anilino] -5-nitroanthra-9,10-quinone, 1,4-dihydroxyanthraquinone, 1,4-bis (4-butylanilino) -5,8-dihydroxyanthraquinone, 4 '-(4-hydroxy-1-anthraquinonylamino) -acetanilide, 1,4-bis [(2,6-diethyl-4-methylphenyl) amino] anthraquinone, 1,4-bis ( Butylamino) -9,10-anthracenedione, 1,4-bis (4-butylanilino) -5,8-dihydroxyanthraquinone, 1,5-bis [(3-methylphenyl) amino] -9 , 10-anthracene On, 1,5-dicyclohexylaminoanthraquinone, 1,4-bis (isopropylamino) anthraquinone, 1,4-bis (methylamino) anthraquinone, 1,4-bis (2,6-diethyl 4-methylanilino) anthraquinone, 2,2 '-(9,10-dioxoanthracene-1,4-diyldiimino) bis (5-methylsulfonate), 1-anilino-4-hydro Roxyantraquinone, 1-hydroxy-4-[(4-methylphenyl) amino] -9,10-anthracenedione, 1,4-bis (para-tolylamino) anthraquinone, 1-amino-4-fetylamino Anthraquinone, N- [4-[(4-hydroxy-anthraquino-1-yl) amino] phenyl] acetamide, 1- (methylamino) -4- (4-methylanilino) anthracene-9,10 -Dione and 1,4,5,8-tetrahydroxyanthraquinone.
In addition to the dispersing aid, it may further comprise a commercially available dispersing aid. Specifically, the SOLSPERSE-5000, SOLSPERSE-12000, SOLSPERSE-22000 of Lubrizol, BYK-SYNERGIST 2100, BYK-SINERGIST 2105, BASF EFKA-6745 or EFKA-6750, etc. may be mentioned.
The dispersing aid comprises 1 to 30 parts by weight based on 100 parts by weight of the pigment in the colorant. When the dispersing aid exceeds 30 parts by weight, the color inherent in the colorant (A) may be altered, and may be discolored by hard baking during the manufacturing process of the colored layer.
(a4) Dispersion solvent
The dispersion solvent is not particularly limited and various organic solvents used in the art may be used.
Specifically, for example, 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, and propylene glycol monomethyl ether acetate , Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, methyl ethyl Ketone, ace Ketones such as methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3-methoxy Ester, such as methyl propionate, Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned. Preferably, alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate can be used, and more preferably propylene glycol monomethyl ether acetate and propylene glycol mono Ethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like can be used.
The said dispersion solvent can be used individually or in mixture of 2 or more types, respectively.
The dispersion solvent is included 60 to 90% by weight, preferably 70 to 85% by weight based on the total weight of the pigment dispersion composition. Outside the above range may cause a disadvantage in that the storage stability of the pigment dispersion composition is poor.
(a5) dispersion resin
The dispersion resin may be selectively added to act as a dispersion medium of the colorant (A), and the mixture of the dispersion resin (a5) may be used to prepare a better pigment dispersion composition than the use of the dispersion agent (a2) alone. In the case of the dispersion resin, it can be used without limitation as long as it can function as a dispersion medium, but it is preferable to have an acid value in order to have solubility in an alkaline developer in consideration of the developability of the colored photosensitive resin composition prepared from the pigment dispersion composition.
The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be determined by titration using an aqueous potassium hydroxide solution.
In the case of the acid-containing dispersion resin, the compound (b1) having an unsaturated bond with the carboxyl group and the compound (b2) having an unsaturated bond copolymerizable with the compound (b1) may be prepared by copolymerizing.
Specific examples of the compound (b1) having a carboxylic acid group and an unsaturated bond 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 the dicarboxylic acids; mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and the like, and acrylic acid and methacrylic acid are preferred.
The compound illustrated by the said compound (b1) can be used individually or in combination of 2 or more types, respectively. Compound (b2) having an unsaturated bond copolymerizable with the compound (b1) may be, for example, styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p -Methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether or p-vinylbenzyl glycid Aromatic vinyl compounds such as dil ether; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate or t-butyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decane-8-yl (meth) acrylate, 2- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate or isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate or benzyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide compounds such as -methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; Unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane or 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. Unsaturated oxetane compounds, and the like, but are not limited thereto.
The compound illustrated by the said compound (b2) can be used individually or in combination of 2 types or more, respectively.
The dispersion resin is included in an amount of 5 to 60 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the pigment solids in the colorant. When the dispersion resin exceeds 60 parts by weight, the viscosity may be increased by the dispersion resin, and when the dispersion resin is less than 5 parts by weight, the amount of the dispersion resin is insufficient to obtain an atomized pigment dispersion composition.
(a6) dye
The dye may be used without limitation so long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye having solubility in an organic solvent and ensuring reliability such as solubility in an alkaline developer, heat resistance and solvent resistance.
The dye may be selected from acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof, and azo, xanthene, and phthalocyanines. Acid dyes and derivatives thereof can also be selected.
Preferably, the dye may be 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).
Specific examples of the dye include C.I. As solvent dyes,
C.I. Solvent yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, and 162;
C.I. Solvent red 8, 45, 49, 122, 125 and 130;
C.I. Solvent oranges 2, 7, 11, 15, 26 and 56;
C.I. Solvent blue 35, 37, 59 and 67;
C.I. Green dyes, such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35, etc. are mentioned.
See also C.I. As an acid dye
CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243 and 251;
CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 , 382, 383, 394, 401, 412, 417, 418, 422 and 426;
C.I. acid oranges 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169 and 173;
CI acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103 , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1 , 335 and 340;
C.I. Acid Violet 6B, 7, 9, 17 and 19;
And dyes such as C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109.
Also as a C.I. direct dye
CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138, and 141;
CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 and 250;
C.I. direct oranges 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106 and 107;
CI direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;
C.I. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104;
And dyes such as C.I.Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82.
In addition, C.I. As modanto dye
C.I. Modanto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 and 65;
CI Modanto Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94 and 95;
C.I. modanto orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 and 48;
CI Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83 and 84;
C.I. modanto violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58;
And dyes such as C.I. modanto green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53.
The colorant (A) may be used in combination of one or more pigments or dyes, respectively. In addition, 0.5 to 25% by weight relative to the total weight of solids in the colored photosensitive resin composition of the present invention, preferably 1 to 20% by weight, more preferably 2 to 15% by weight.
Alkali-soluble resin (B)
Alkali-soluble resins can use those known in the art. In particular, it is preferable to include at least one of the compounds consisting of the following formulas 4 to 7, wherein the compounds of formulas 4 to 7 are each 3 to 80 mol%, preferably 5, in mole fraction with respect to the total number of moles of alkali-soluble resin, respectively. To 70 mol%. When at least one of the compounds of Formulas 4 to 7 is included within the mole fraction range, the sensitivity and adhesion of the colored photosensitive resin composition may be excellent, and thus peeling of the pattern may not occur during the developing process, and solvent resistance may be excellent.
[Formula 4]
[Formula 5]
[Formula 6]
[Formula 7]
An alkali-soluble resin having at least one unit selected from the group consisting of Chemical Formulas 4 to 7 may be prepared by polymerizing with a polymerizable compound.
Specific examples of the unsaturated bond copolymerizable with the chemical formulas 4 to 7 of the alkali-soluble resin include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, and p-methoxy Styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like. Aromatic vinyl compounds; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decane-8-yl (meth) acrylate, 2- Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 3,4-epoxytricyclodecane-8-yl (meth) acrylate, 3,4-epoxytricyclodecane-9-yl Alicyclic (meth) acrylates such as (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide compounds such as -methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; (meth) acrylamide, Unsaturated amide compounds such as N, N-dimethyl (meth) acrylamide; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. And unsaturated oxetane compounds.
The compounds exemplified above may be used alone or in combination of two or more thereof.
The alkali-soluble resin of the present invention may be used by further mixing various known alkali-soluble resins commonly used in the art as needed.
The alkali-soluble resin has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, preferably 5,000 to 50,000. If the weight average molecular weight of the alkali-soluble resin is outside the above range, the film reduction is not prevented at the time of development, causing a problem that the omission of the pattern portion may occur.
The acid value of the alkali-soluble resin is 50 to 150 (KOH mg / g), preferably 60 to 140 (KOH mg / g), more preferably 80 to 135 (KOH mg / g), most preferably Is 80 to 130 (KOH mg / g). When the acid value of the said alkali-soluble resin is 50-150 (KOHmg / g), solubility to a developing solution improves and a residual film rate improves.
The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be determined by titration using an aqueous potassium hydroxide solution.
The alkali-soluble resin includes 10 to 80% by weight, preferably 10 to 70% by weight based on the total weight of solids in the colored photosensitive resin composition of the present invention. In the above range, the solubility of the developing solution is sufficient, so that pattern formation is easy, and the film reduction of the pixel portion of the exposed portion is prevented at the time of development, so that the non-pixel portion has good omission.
Photopolymerizable Compound (C)
The photopolymerizable compound is not particularly limited as long as it is a compound that can be polymerized by the action of the photopolymerization initiator (D) described later, but is preferably a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, a trifunctional or higher polyfunctional photopolymerizable compound, or the like. Can be mentioned.
Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl py. Commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nipbon Kayaku), or Biscotti 158 (Osaka Yuki Kagaku High School).
Specific examples of the bifunctional monomers include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like; commercially available products such as Aronix M-210, M-1100, 1200 (Doagosei), KAYARAD HDDA (Nipbon Kayaku), Biscot 260 (Osaka Yuki Kagaku High School), AH-600, AT-600 or UA-306H (Kyoeisha Kagakusa).
Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trimethylolpropane tri (meth) acrylate. , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxysilane Tied dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are commercially available products such as Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD. DPHA-40H (Nippon Kayaku).
Among the photopolymerizable compounds exemplified above, trifunctional or more than trifunctional (meth) acrylic acid esters and urethane (meth) acrylates are particularly preferable in terms of excellent polymerizability and improving strength.
Said photopolymerizable compound can be used individually or in combination of 2 or more types, respectively.
The photopolymerizable compound is preferably contained in 5 to 50% by weight, 7 to 48% by weight relative to the total weight of solids in the colored photosensitive resin composition of the present invention. When the photopolymerizable compound is included in the above range, the intensity and smoothness of the pixel portion are good.
Photopolymerization Initiator (D)
As long as it can superpose | polymerize a photopolymerizable compound (C), a photoinitiator can be used without a restriction | limiting in particular.
In particular, the photopolymerization initiator may be an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound, or a thioxanthone compound in view of polymerization characteristics, start efficiency, absorption wavelength, availability, or price. Preference is given to using at least one compound selected from the group consisting of compounds.
Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy 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] propane-1 -One or 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.
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 or 2,4,6-trimethylbenzophenone.
Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6 -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -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 or 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.
Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro Phenyl) -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, The imidazole compound etc. which the phenyl group of a 4'5,5'- tetraphenyl- 1,2'- biimidazole or a 4,4 ', 5,5' position are substituted by the carboalkoxy group are mentioned. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.
Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and OXE-01 and OXE-02 manufactured by BASF are typical examples of the commercially available product.
As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. There is this.
Moreover, photoinitiators other than the photoinitiator mentioned above can also be used within the range which does not impair the effect of this invention. For example, a benzoin type compound, an anthracene type compound, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.
Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.
Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. have.
Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl or titanocene compounds, etc. can be used further as a photoinitiator.
In addition, the photopolymerization initiator may further include a photopolymerization initiation aid (D-1) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition which concerns on this invention can contain a photoinitiation adjuvant (D-1), and can improve a sensitivity and improve productivity.
As the photopolymerization initiation assistant (D-1), for example, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds and organic sulfur compounds having thiol groups can be preferably used.
It is preferable to use an aromatic amine compound as the amine compound, and specifically, aliphatic amine compounds such as triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone ) Or 4,4'-bis (diethylamino) benzophenone can be used.
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 or naphthoxyacetic acid, and the like.
Specific examples of the organic sulfur compound having the 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) -trione, trimethylolpropanetris (3-mergaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl Late), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. are mentioned. Can be.
The photopolymerization initiator may be included in an amount of 0.1 to 10% by weight based on the total weight of solids in the colored photosensitive resin composition based on solids. When included in the above range, the colored photosensitive resin composition may be highly sensitive to shorten the exposure time, thereby improving productivity and maintaining high resolution. In addition, the strength of the pixel portion formed using the composition under the above-described conditions and smoothness on the surface of the pixel portion can be improved.
In addition, when the photopolymerization initiation aid (D-1) is further used, it is preferable to use the same content range as the photopolymerization initiator (D), and when used in the above range, the sensitivity of the colored photosensitive resin composition is increased, The productivity of the colored layer formed using the composition can be provided.
Solvent (E)
As long as the solvent is effective to dissolve the other components included in the colored photosensitive resin composition, the solvent used in the conventional colored photosensitive resin composition can be used without particular limitation, and in particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters Or amides are preferable.
Specifically, the solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, di Ethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, Ethers such as dipropylene glycol dibutyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-meth Methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate or γ-buty Rockactone, etc. And esters thereof.
The solvent is preferably an organic solvent having a boiling point of 100 ° C. to 200 ° C. in terms of coatability and dryness, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalac Tate, 3-ethoxy propionate, methyl 3-methoxypropionate, etc. can be used.
The solvents exemplified above may be used alone or in combination of two or more thereof.
The solvent may be included 40 to 90% by weight, preferably 50 to 85% by weight relative to the total weight of the colored photosensitive resin composition of the present invention. In the said range, when it apply | coats with coating apparatuses, such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes called a die coater), or an inkjet, the applicability | paintability becomes favorable.
<Electronic device>
This invention provides the electronic element manufactured from the said coloring photosensitive resin composition, and the image display apparatus containing the said electronic element.
The electronic device is not particularly limited as long as it is made of a colored photosensitive resin composition, and examples thereof include color filters, black matrices, column spacers, and the like.
Examples of the image display device that may include the electronic device may include a liquid crystal display device, an OLED, a flexible display, and the like, but are not limited thereto, and all image display devices known in the art may be illustrated.
An electronic device can be manufactured by apply | coating the coloring photosensitive resin composition of this invention mentioned above on a base material, photocuring and developing, and forming a pattern.
First, after apply | coating a coloring photosensitive resin composition to a board | substrate, heating and drying remove volatile components, such as a solvent, and obtain a smooth coating film.
As a coating method, it can carry out by a spin coat, cast coating method, the roll coating method, the slit and spin coat, the slit coat method, etc., for example. After coating, heating and drying (prebaking) or drying under reduced pressure are carried out to volatilize volatile components such as a solvent. Here, heating temperature is 70-200 degreeC normally, Preferably it is 80-130 degreeC. The coating film thickness after heat drying is about 1-8 micrometers normally. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that the parallel light beam may be irradiated uniformly to the whole exposure part, and the exact alignment of a mask and a board | substrate is performed. When ultraviolet light is irradiated, curing of the site irradiated with ultraviolet light is performed.
G-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm) and the like can be used as the ultraviolet rays. The irradiation amount of ultraviolet rays may be appropriately selected as necessary, and the present invention is not limited thereto. When the coating film after hardening is contacted with a developing solution and the non-exposed part is melted and developed, the target pattern shape can be formed.
The developing method may be any of a liquid addition method, a dipping method, a spray method and the like. In addition, during development, the substrate may be tilted at an arbitrary angle. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate And sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine and the like.
These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.
The surfactant in the alkaline developer may be at least one selected from the group consisting of nonionic surfactants, anionic surfactants or cationic surfactants.
Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.
Specific examples of the anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.
Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts. These surfactant can be used individually or in combination of 2 or more types, respectively.
The concentration of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight. After image development, it is washed with water and also 10-60 minutes post-baking may be performed at 150-230 degreeC as needed.
Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.
Synthesis Example : Alkali Soluble Resin Manufacturing
A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared. As the monomer dropping lot, 40 parts by weight of a mixture of 3,4-epoxytricyclodecane-8-yl acrylate and 3,4-epoxytricyclodecane-9-yl acrylate in a molar ratio of 50:50, methylmethacryl 50 parts by weight of rate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyltoluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) were added to prepare stirring. . As a chain transfer agent dropping tank, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added to prepare agitation. Thereafter, 395 parts by weight of PGMEA was added to the flask, the atmosphere in the flask was exchanged with nitrogen in air, and the temperature of the flask was raised to 90 ° C. while stirring. The monomer and chain transfer agent were then started dropping from the dropping lot. The dropwise addition was performed for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 5 hours to obtain a resin (B-1) having a solid acid value of 75 mgKOH / g.
The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of alkali-soluble resin was measured on condition of the following by GPC method.
HLC-8120GPC (manufactured by Tosoh Corporation) was used. The TSK-GELG4000HXL and TSK-GELG2000HXL columns were used in series, and the temperature of the column was 40 ° C. Tetrahydrofuran was used as the mobile phase solvent and measured at a flow rate of 1.0 mL / min. The concentration of the measurement sample was 0.6% by weight, the injection amount was 50 µL, and analyzed using a RI detector. TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation) were used as calibration standard materials, and the weight average molecular weight and number of alkali-soluble resins obtained under the above conditions. Average molecular weight was measured.
The weight average molecular weight of polystyrene conversion measured by gel permeation chromatography was 17,000 (g / mol), and molecular weight distribution (Mw / Mn) was 2.3.
Example
A colored photosensitive resin composition was prepared with the components and contents shown in Table 1 below.
(A)
(B)
(C)
(D)
(E)
(F)
PB16
PR179
11
13
PB60
PR179
14
11
PB16
PB60
PR179
8
4
12
PB15: 6
PR179
12
13
PB16: Pigment Blue 16 (manufactured by Ciba)
PB60: Pigment Blue 60 (manufactured by Ciba)
PB15: 6: Pigment Blue 15: 6 (made by DIC Corporation)
PR179: Pigment Red 179 (EP-193, manufactured by DIC Corporation)
B: Alkali-soluble resin of Synthesis Example
C: dipentaerythritol hexaacrylate (Kayarad DPHA: manufactured by Nippon Kayaku Co., Ltd.)
D: ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE -02: manufactured by BASF Corporation
E: Propylene Glycol Monomethyl Ether Acetate
F-1: DiperBYK-163 (by BYK Corporation)
Experimental Example
A glass substrate of 5 cm x 5 cm (Corning # 1737) was washed with a neutral detergent and water and dried. The glass substrate was spin-coated so that the final film thickness might be 3.0 µm, and dried at 80 to 120 ° C. for 1 to 2 minutes to remove the solvent. Thereafter, a 2 cm × 2 cm pattern is formed by exposing at an exposure dose of 40 to 100 mJ / cm 2, and the non-exposed part is removed using an alkaline aqueous solution. Subsequently, firing was performed by firing at 200 to 250 ° C. for 10 to 30 minutes.
1. Metal Dissolution Analysis
The substrate was precipitated in 15 g of normal methyl pyrrolidone (NMP, N-Methyl-2-pyrrolidone), and precipitated at 100 ° C. for 3 hours to elute from the substrate. Then, ICP-MS was used to check the metal content of NMP. do. Measurements were made using an Agilent 7700 instrument at Flow 0.91 L / min.
2. Transmittance Measurement
The transmittance at Near-IR was measured using a UV-vis spectrometer (UV-2550, Shimazu Co., Ltd.). The measurement results are summarized in the table below, and the absorption areas at 380 to 780 nm are integrated and listed in Table 2.
Referring to Table 2, Examples of the present invention can be seen that the amount of the metal eluted significantly less than the comparative example. Thereby, the influence on the display liquid crystal drive can be reduced.
In addition, it can be seen that the transmittance measurement result also has a larger absorption area than the comparative example. It can be seen that the color characteristic, which is an important characteristic of the present invention, is improved.
Claims (7)
Said (A) coloring agent contains the mixture of at least 1 sort (s) of a pigment blue 16 and a pigment blue 60, and a black pigment,
The mixing weight ratio of at least one of Pigment Blue 16 and Pigment Blue 60 and the black pigment is 1: 0.15 to 1: 3,
Colored photosensitive resin composition for column spacer formation which does not contain Pigment Blue 15: 6.
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| KR1020130103607A KR102028580B1 (en) | 2013-08-30 | 2013-08-30 | Colored photosensitive resin composition for forming column spacer |
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| JP6704337B2 (en) * | 2015-12-28 | 2020-06-03 | 住友化学株式会社 | Colored photosensitive resin composition, color filter and display device including the same |
| TWI721087B (en) * | 2016-01-27 | 2021-03-11 | 日商住友化學股份有限公司 | Colored curable resin composition, color filter and display device including same |
| JP6837863B2 (en) * | 2017-02-17 | 2021-03-03 | 住友化学株式会社 | Red coloring composition |
| KR102157142B1 (en) * | 2017-10-20 | 2020-09-17 | 동우 화인켐 주식회사 | A black photo sensitive resin composition, a color filter comprising a black metrics and/or a column spacer prepared by using the composition, and a display comprising the color filter |
| KR101840984B1 (en) * | 2017-11-10 | 2018-03-21 | 동우 화인켐 주식회사 | A photo sensitive resin composition, a color filter comprising a black metrics, a column spacer or black column spacer prepared by using the composition, and a display device comprising the color filter |
| KR101923832B1 (en) * | 2017-11-20 | 2019-02-27 | 동우 화인켐 주식회사 | Photosensitive resin composition, and pattern formed therefrom, color filter comprising thereof and liquid crystal display device comprigin the color filter |
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| JP2004219979A (en) * | 2002-12-25 | 2004-08-05 | Mitsubishi Chemicals Corp | Colored photosensitive composition, color filter, and liquid crystal display device formed by using the same |
| JP2004285281A (en) | 2003-03-24 | 2004-10-14 | Dainippon Printing Co Ltd | Auxiliary dispersant polymer for colored resist, pigment dispersion for colored resist, photosensitive colored composition, and color filter |
| JP2005165294A (en) | 2003-11-11 | 2005-06-23 | Mitsubishi Chemicals Corp | Curable composition, cured object, color filter and liquid-crystal display |
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| KR20100066197A (en) | 2008-12-09 | 2010-06-17 | 제일모직주식회사 | Black photosensitive resin composition, and black matrix and column spacer using the same |
| KR101805197B1 (en) * | 2011-11-02 | 2017-12-07 | 동우 화인켐 주식회사 | A colored photosensitive resin composition, colored pattern,color filter and liquid crystal display device having the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004219979A (en) * | 2002-12-25 | 2004-08-05 | Mitsubishi Chemicals Corp | Colored photosensitive composition, color filter, and liquid crystal display device formed by using the same |
| JP2004285281A (en) | 2003-03-24 | 2004-10-14 | Dainippon Printing Co Ltd | Auxiliary dispersant polymer for colored resist, pigment dispersion for colored resist, photosensitive colored composition, and color filter |
| JP2005165294A (en) | 2003-11-11 | 2005-06-23 | Mitsubishi Chemicals Corp | Curable composition, cured object, color filter and liquid-crystal display |
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