CN110297393B - Colored photosensitive resin composition, color filter comprising same, and image display device - Google Patents
Colored photosensitive resin composition, color filter comprising same, and image display device Download PDFInfo
- Publication number
- CN110297393B CN110297393B CN201910195354.9A CN201910195354A CN110297393B CN 110297393 B CN110297393 B CN 110297393B CN 201910195354 A CN201910195354 A CN 201910195354A CN 110297393 B CN110297393 B CN 110297393B
- Authority
- CN
- China
- Prior art keywords
- resin composition
- photosensitive resin
- colored photosensitive
- acrylate
- pigment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- 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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Liquid Crystal (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a colored photosensitive resin composition, a color filter and an image display device including the same, wherein the colored photosensitive resin composition includes a non-reactive alkali-soluble resin and a photopolymerization initiator (A), and the photopolymerization initiator (A) includes a photopolymerization initiator (a1) having two oxime groups in one molecule, so that a pattern shape can be realized in a form of a positive slope (top) after a post-baking process in a color filter process, and thus, a problem in a manufacturing process does not occur and a hole (hole) can be prevented from being generated in the formed pattern.
Description
Technical Field
The present invention relates to a colored photosensitive resin composition, a color filter comprising the colored photosensitive resin composition, and an image display device.
Background
As a method for forming a color filter using the colored photosensitive resin composition, the following methods are mainly used: a coating film of a colored photosensitive resin composition is formed on a substrate or a substrate on which a light shielding layer of a desired pattern is formed in advance, and then light is irradiated (hereinafter, referred to as exposure) through a photomask having a predetermined pattern, and the light is developed to dissolve and remove an unexposed portion, and then post-baking is performed, thereby obtaining pixels of respective colors.
In addition, in recent years, in the field of color filter technology, in order to reduce the exposure dose and shorten the Tact time (Tact time) and to meet the recent demand for higher color purity of image display devices, there is a tendency that the content (ratio) of the colorant in the colored photosensitive resin composition is increased, whereby the content of components other than the colorant is decreased, and there is a possibility that problems such as a decrease in adhesion and generation of residue during the production of a color filter occur.
In connection with this, patent document 1 describes a photosensitive resin composition for a color filter and a color filter using the photosensitive resin composition, the photosensitive resin composition for color filters is characterized by comprising an alkali-soluble resin, an acrylic photopolymerizable monomer, a photopolymerization initiator, a pigment and a solvent, the alkali-soluble resin is a copolymer of a) an ethylenically unsaturated monomer containing one or more double bonds represented by a specific chemical formula, b) an ethylenically unsaturated monomer having one or more carboxyl groups, and c) an ethylenically unsaturated monomer copolymerizable with the monomer of b), thereby, a color filter having no residue, excellent adhesion, and high resolution and composed of ultra-fine pixels can be manufactured, however, when a color filter is produced using such a composition, there is a problem that a pattern is formed in a reverse slope form before a subsequent heat treatment step (post-baking), and a step error occurs.
Documents of the prior art
Patent document
Patent document 1: korean patent registration No. 10-0875269
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a colored photosensitive resin composition which can form a pattern in the form of a positive slope after a post-baking step which is a high-temperature heat treatment in a color filter production process, and which does not cause a problem in the process, and a color filter and an image display device each including the colored photosensitive resin composition.
Means for solving the problems
The colored photosensitive resin composition of the present invention for achieving the above object is characterized by comprising a non-reactive alkali-soluble resin and a photopolymerization initiator (a) which comprises a photopolymerization initiator (a1) having two oxime groups in one molecule.
The color filter of the present invention is characterized by containing a cured product of the colored photosensitive resin composition.
The image display device of the present invention includes the color filter.
Effects of the invention
The colored photosensitive resin composition of the present invention has an advantage that the shape of the pattern can be realized in the form of a straight slope after the post-baking step in the color filter manufacturing process, and thus problems in the manufacturing process do not occur.
The color filter of the present invention has the same advantages as described above.
The image display device of the present invention has the same advantages as those described above.
Drawings
Fig. 1 to 3 are diagrams illustrating a process of manufacturing a color filter.
Fig. 4 is a diagram showing a method for determining the pattern slope form.
Description of the symbols
10: substrate
11: color layer
11R: colour pattern
20: photomask and method of manufacturing the same
30: light (es)
Detailed Description
In the present invention, when a member is referred to as being "on" another member, it includes not only a case where the member is in contact with the another member but also a case where the another member is present between the two members.
In the present invention, when a part is referred to as "including" a certain component, it means that other components may be further included without excluding other components unless otherwise stated.
The present invention will be described in more detail below.
< colored photosensitive resin composition >
The colored photosensitive resin composition according to one embodiment of the present invention is characterized by comprising a non-reactive alkali-soluble resin and a photopolymerization initiator (a) containing a photopolymerization initiator (a1) having two oxime groups in one molecule, and is capable of realizing a pattern shape in the form of a positive slope (top) after a post-baking step in a color filter step, and thus has an advantage of preventing problems in a manufacturing process and an advantage of preventing the formation of holes (holes) in the formed pattern.
Non-reactive alkali soluble resin
The colored photosensitive resin composition according to one embodiment of the present invention has an advantage that the shape of a color pattern formed in the production of a color filter can be realized in the shape of a normal slope by including a non-reactive alkali-soluble resin.
According to an embodiment of the present invention, the glass transition temperature of the non-reactive alkali-soluble resin may be 0 ℃ or lower, and the weight average molecular weight may be 3,000 to 12,000. In this case, the weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC; using tetrahydrofuran as an eluting solvent). The weight average molecular weight may be preferably 6,000 to 10,000, and when the weight average molecular weight is within the range disclosed in the present invention, there are advantages in that the hardness of the pattern is increased, the film remaining ratio (film remaining ratio) is increased, and the solubility and resolution of the non-exposed portion in the developer are improved.
In addition, according to an embodiment of the present invention, the non-reactive alkali-soluble resin may specifically contain no epoxy group or unsaturated double bond in the molecule.
According to an embodiment of the present invention, the non-reactive alkali-soluble resin having a glass transition temperature of 0 ℃ or less may include 10 to 50% by weight, preferably 15 to 40% by weight of repeating units of a compound having a glass transition temperature of 0 ℃ or less derived from a homopolymer, and the compound may be, specifically, one or more compounds selected from the group consisting of ethyl acrylate, n-butyl acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl acrylate, and lauryl (meth) acrylate, but is not limited thereto.
The non-reactive alkali-soluble resin may specifically be a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the above monomer.
Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids having one or more carboxyl groups in the molecule, such as unsaturated tricarboxylic acids. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α -chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polycarboxylic acid may be a mono (2-methacryloxyalkyl) ester thereof, and examples thereof include mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate, mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxylic polymer at both ends thereof, and examples thereof include ω -carboxy polycaprolactone monoacrylate, ω -carboxy polycaprolactone monomethacrylate and the like. The carboxyl group-containing monomers may be used singly or in combination of two or more.
Examples of the other monomer copolymerizable with the carboxyl group-containing monomer include aromatic vinyl compounds such as ethylenically unsaturated monomers having a double bond, styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, indene, and the like; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, n-butyl acrylate, isopropyl acrylate, isobutyl acrylate, butyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, unsaturated carboxylic acid esters such as 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; aminoalkyl esters of unsaturated carboxylic acids such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α -chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and macromonomers having a monoacryloyl group or monomethacryloyl group at the end of a polymer molecular chain of polysiloxane. These monomers may be used either individually or as a mixture of two or more thereof.
Specific examples of the non-reactive alkali-soluble resin include (meth) acrylic acid/methyl (meth) acrylate/2-ethylhexyl (meth) acrylate copolymers, (meth) acrylic acid/benzyl (meth) acrylate/2-ethylhexyl (meth) acrylate copolymers, (meth) acrylic acid/2-hydroxyethyl (meth) acrylate/benzyl (meth) acrylate/2-ethylhexyl (meth) acrylate copolymers, (meth) acrylic acid/benzyl (meth) acrylate/N-phenylmaleimide/2-ethylhexyl (meth) acrylate copolymers, (meth) acrylic acid/2-ethylhexyl (meth) acrylate/styrene/benzyl (meth) acrylate copolymers, Examples of the (meth) acrylic acid/succinic acid mono (2-acryloyloxyethyl) ester/styrene/2-ethylhexyl (meth) acrylate copolymer, and examples of the (meth) acrylic acid/benzyl (meth) acrylate/2-ethylhexyl (meth) acrylate/glycerol mono (meth) acrylate copolymer include, but are not limited to, these.
In the present specification, the term (meth) acrylate refers to acrylate and/or methacrylate.
According to an embodiment of the present invention, the acid value of the non-reactive alkali-soluble resin may be 20 to 200 mgKOH/g. When the acid value satisfies the above range, the solubility in a developer is increased, the unexposed portion is easily dissolved, the sensitivity is increased, and as a result, a pattern at the exposed portion is left during development, and therefore, there is an advantage that the film retention rate can be improved. In this case, the acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the acrylic polymer, and can be usually determined by titration with an aqueous solution of potassium hydroxide.
According to one embodiment of the present invention, the content of the non-reactive alkali-soluble resin may be 10 to 80 parts by weight, preferably 20 to 70 parts by weight, based on 100 parts by weight of the total solid content in the colored photosensitive resin composition containing the non-reactive alkali-soluble resin. In the case where the content of the alkali-soluble resin is within the above range, there are advantages in that a color pattern can be formed, and resolution and film retention can be improved.
Photopolymerization initiator (A)
The colored photosensitive resin composition according to one embodiment of the present invention has an advantage that the shape of the pattern is realized in the form of a positive slope after the post-baking step in the production of the color filter by including the photopolymerization initiator (a1) having two oxime groups in one molecule.
In addition, according to an embodiment of the present invention, the photopolymerization initiator (a1) may have a molecular weight of 400 to 750. When the molecular weight is satisfied, there is an advantage that the positive slope can be more easily realized.
The photopolymerization initiator (a1) may specifically include one or more compounds selected from the group consisting of compounds represented by the following chemical formulas 1 to 7.
[ chemical formula 1]
[ chemical formula 2]
[ chemical formula 3]
[ chemical formula 4]
[ chemical formula 5]
[ chemical formula 6]
[ chemical formula 7]
The photopolymerization initiator (a1) of the present invention can be used after being synthesized by a conventional method by a person having ordinary skill in organic chemistry knowledge, or can be used by purchasing a commercially available product.
According to an embodiment of the present invention, the colored photosensitive resin composition of the present invention may further include a photopolymerization initiator (a2) other than the photopolymerization initiator (a 1).
The photopolymerization initiator (a2) is not particularly limited as long as it can polymerize a photopolymerizable compound to be described later, and examples thereof include acetophenone type, benzoin type, benzophenone type, thioxanthone type, triazine type, oxime type, and the like,
Salts, nitrobenzyl tosylate, benzoin tosylate and the like. Examples of the acetophenone-based compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] ketal]Propane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl]Oligomers of propan-1-one, etc., more preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one. In addition, a plurality of acetophenone compounds and other photopolymerization initiators may be used in combination. Examples of the photopolymerization initiator other than the acetophenone-based compound include an active radical generator, a sensitizer, an acid generator, and the like, which generate active radicals by irradiation with light. Examples of the active radical generating agent include benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds. Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and,Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like. Examples of the benzophenone-based compound include benzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethylene]-1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethylene]-1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethylene]-1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) ethylene]-1,3, 5-triazine and the like. Examples of the oxime compound include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl]-1, 2-octanedione, 1- (4-methylsulfonyl-phenyl) -butane-1, 2-butane-2-oxime-O-acetate, 1- (4-methylsulfonyl-phenyl) -butane-1-ketoxime-O-acetate, hydroxyimino- (4-methylsulfonyl-phenyl) -acetic acid ethyl ester-O-benzoate, and the like. Examples of the sensitizer include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2-bis (o-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzil, 9, 10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compound. Examples of the acid generator include 4-hydroxyphenyldimethylsulfide
P-toluenesulfonate, 4-hydroxyphenyl dimethylsulfide
Hexafluoroantimonate, 4-acetoxyphenyl dimethyl sulfide
P-toluenesulfonate, 4-acetoxyphenyl methylbenzylthio
Hexafluoroantimonate, triphenylsulfur
P-toluenesulfonate salt, triphenylsulfur
Hexafluoroantimonate and diphenyl iodide
P-toluenesulfonate and diphenyliodine
Hexafluoroantimonate and the like
Salts, nitrobenzyl tosylates, benzoin tosylates, and the like. In addition, there are also compounds that generate active radicals and acids simultaneously among the above compounds. For example, the triazine-based photopolymerization initiator may be used as an acid generator.
The content of the entire photopolymerization initiator (a) may be 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the entire solid content in the colored photosensitive resin composition containing the photopolymerization initiator (a). When the content of the photopolymerization initiator (a) is within the above range, there is an advantage that the sensitivity is improved and the exposure time is shortened, so that the productivity can be improved and the high resolution can be maintained.
The colored photosensitive resin composition of the present invention may further contain a photopolymerization initiator, if necessary. The photopolymerization initiator (a) may be used in combination with the photopolymerization initiator (a) in some cases, and may be used to promote polymerization of the photopolymerizable compound initiated by the photopolymerization initiator (a). Examples of the photopolymerization initiation assistant include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and the like. Examples of the amine-based compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4 '-bis (ethylmethylamino) benzophenone and the like, and among them, 4' -bis (diethylamino) benzophenone is preferable. Examples of the alkoxyanthracene compound include 9, 10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, and 2-ethyl-9, 10-diethoxyanthracene. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. The photopolymerization initiator may be used alone or in combination of two or more. Further, as the photopolymerization initiation assistant, a commercially available product may be used, and as the commercially available photopolymerization initiation assistant, for example, EAB-F (product of guayu chemical industries) or the like is available. Examples of the combination of the photopolymerization initiator and the photopolymerization initiation aid which is preferable for the colored photosensitive resin composition of the present invention include diethoxyacetophenone/4, 4 '-bis (diethylamino) benzophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one/4, 4' -bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-phenylpropan-1-one/4, 4 '-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one/4, 4' -bis (diethylamino) benzophenone, and mixtures thereof, Combinations of 1-hydroxycyclohexyl phenyl ketone/4, 4 ' -bis (diethylamino) benzophenone, oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one/4, 4 ' -bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one/4, 4 ' -bis (diethylamino) benzophenone, and the like, more preferably, a combination of 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and 4, 4' -bis (diethylamino) benzophenone is used. When the photopolymerization initiator and the photopolymerization initiation aid are used together as described above, the amount of the photopolymerization initiation aid used is preferably 10 moles or less, more preferably 0.01 to 5 moles per 1 mole of the photopolymerization initiator.
The colored photosensitive resin composition according to an embodiment of the present invention may further include one or more selected from the group consisting of a colorant, a photopolymerizable compound, a solvent, and an additive.
Coloring agent
The colorant is configured to be applied in various ways according to the use of the color filter, and the type thereof is not particularly limited in the present invention.
The colorant may be any of pigments, dyes, or natural pigments, and as The Pigment, a compound classified as a Pigment (Pigment) in The color index (published by The Society of Dyers and Colourists) may be used. The colorant of the present invention is preferably an organic pigment in view of excellent heat resistance and color developability.
Specific examples of preferred pigments usable in the present invention include:
c.i. pigment yellow 1, c.i. pigment yellow 3, c.i. pigment yellow 12, c.i. pigment yellow 13, c.i. pigment yellow 14, c.i. pigment yellow 15, c.i. pigment yellow 16, c.i. pigment yellow 17, c.i. pigment yellow 20, c.i. pigment yellow 24, c.i. pigment yellow 31, c.i. pigment yellow 53, c.i. pigment yellow 83, c.i. pigment yellow 86, c.i. pigment yellow 93, c.i. pigment yellow 94, c.i. pigment yellow 109, c.i. pigment yellow 110, c.i. pigment yellow 117, c.i. pigment yellow 125, c.i. pigment yellow 128, c.i. pigment yellow 137, c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 147, c.i. pigment yellow 148, c.i. pigment yellow 150, c.i. pigment yellow 153, c.i. pigment yellow 154, c.i. pigment yellow 194, c.i. pigment yellow 173, c.i. pigment yellow 214;
orange pigments such as c.i. pigment orange 13, c.i. pigment orange 31, c.i. pigment orange 38, c.i. pigment orange 40, c.i. pigment orange 42, c.i. pigment orange 43, c.i. pigment orange 51, c.i. pigment orange 55, c.i. pigment orange 59, c.i. pigment orange 61, c.i. pigment orange 64, c.i. pigment orange 65, c.i. pigment orange 71, c.i. pigment orange 73;
red pigments such as c.i. pigment red 9, c.i. pigment red 97, c.i. pigment red 105, c.i. pigment red 122, c.i. pigment red 123, c.i. pigment red 144, c.i. pigment red 149, c.i. pigment red 166, c.i. pigment red 168, c.i. pigment red 176, c.i. pigment red 177, c.i. pigment red 180, c.i. pigment red 192, c.i. pigment red 209, c.i. pigment red 215, c.i. pigment red 216, c.i. pigment red 224, c.i. pigment red 242, c.i. pigment red 254, c.i. pigment red 264, and c.i. pigment red 265;
blue pigments such as c.i. pigment blue 15, c.i. pigment blue 15:3, c.i. pigment blue 15:4, c.i. pigment blue 15:6, c.i. pigment blue 60, and the like;
violet pigments such as c.i. pigment violet 1, c.i. pigment violet 19, c.i. pigment violet 23, c.i. pigment violet 29, c.i. pigment violet 32, c.i. pigment violet 36, and c.i. pigment violet 38;
green pigments such as c.i. pigment green 7, c.i. pigment green 36, and c.i. pigment green 58;
brown pigments such as c.i. pigment brown 23 and c.i. pigment brown 25;
black pigments such as c.i. pigment black 1 and c.i. pigment black 7.
Among them, it is preferable to contain one or more pigments selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 150, c.i. pigment red 177, c.i. pigment red 209, c.i. pigment red 254, c.i. pigment violet 23, c.i. pigment blue 15:6, and c.i. pigment green 36.
The organic pigment and the inorganic pigment may be used alone or in combination. For example, it is preferable to include c.i. pigment red 254 and c.i. pigment yellow 139 in forming a red pixel, c.i. pigment green 58, c.i. pigment yellow 150, or c.i. pigment yellow 138 in forming a green pixel, and c.i. pigment blue 15:6 in forming a blue pixel, respectively, but the present invention is not limited thereto.
The dye of the present invention may be used in any amount without limitation as long as it has solubility in an organic solvent. It is preferable to use a dye having solubility in an organic solvent and capable of ensuring solubility in an alkali developing solution and reliability such as heat resistance and solvent resistance. As the dye, a dye selected from an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye with a nitrogen-containing compound, a sulfonamide of an acid dye, and derivatives thereof may be used, and in addition thereto, an azo-based, xanthene-based, phthalocyanine-based acid dye, and derivatives thereof may be selected. The dyes include compounds classified as dyes by The color index (The Society of Dyers and Colourists) or known dyes described in The color handbook (Dyers).
Specific examples of the above dye include c.i. solvent dyes:
c.i. yellow dyes such as solvent yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, etc.;
c.i. solvent red 8, 45, 49, 122, 125, 130 and the like red dyes;
orange dyes such as c.i. solvent orange 2, 7, 11, 15, 26, 45, 56, 62, etc.;
c.i. blue dyes such as solvent blue 35, 37, 45, 59, 67;
c.i. solvent green 1,3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and the like.
Further, as the c.i. acid dye, there may be mentioned:
c.i. yellow dyes such as 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, 251;
c.i. acid red 1,4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426, etc. red dye;
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, etc.;
c.i. 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, 340 and the like blue dye;
c.i. violet dyes such as acid violet 6B, 7, 9, 17, 19, etc.;
c.i. acid green 1,3,5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, and the like.
Further, as the c.i. direct dye, there can be mentioned:
c.i. 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, 141 and the like;
c.i. direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250 and the like red dye;
c.i. direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, etc. orange dyes;
c.i. 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, 293, and the like blue dye;
c.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 and the like violet dye;
c.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc.
Further, as the c.i. mediator dye, there may be mentioned:
yellow dyes such as c.i. mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 and the like;
c.i. medium 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, 95 and the like red dye;
c.i. intermediate orange 3,4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 and other orange dyes;
c.i. medium 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, 84 and the like blue dye;
c.i. intermediate violet 1,2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58 and the like violet dye;
c.i. medium green 1,3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like.
The content of the colorant is 10 to 70 parts by weight, preferably 20 to 60 parts by weight, based on 100 parts by weight of the total solid content in the colored photosensitive resin composition containing the colorant. When the content of the colorant is within the above range, the color density is sufficient when the color filter is produced, and a pattern having sufficient mechanical strength can be formed.
In the present invention, the solid content of the colored photosensitive composition means the total amount of components obtained by removing the solvent.
The organic pigment of the above pigments may be subjected to the following treatments as required: surface treatment using a pigment derivative into which an acidic group or a basic group is introduced; graft treatment of the pigment surface with a polymer compound or the like; micronization treatment by sulfuric acid micronization (refining); washing treatment with an organic solvent or water for removing impurities; or removal treatment by an ion exchange method using ionic impurities. The colorant is preferably uniform in particle size. When the colorant is a pigment, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained by adding a pigment dispersant and performing dispersion treatment.
The pigment is preferably used in the form of a pigment dispersion liquid in which the particle diameter is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of performing a dispersion treatment by adding a pigment dispersant, and according to this method, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained.
Specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants, and these may be used alone or in combination of two or more.
The pigment dispersant is added for the purpose of disaggregation and maintenance of stability of the pigment, and any pigment dispersant generally used in the art can be used without limitation. It is preferable to contain an acrylate-based dispersant (hereinafter, referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate). In this case, it is preferable to use a dispersant produced by an activity control method as disclosed in Korean patent laid-open No. 2004-0014311, and examples of commercially available acrylate dispersants produced by the activity control method include, but are not limited to, DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150, and they may be used alone or in combination of two or more kinds.
The dispersant may be a resin type pigment dispersant other than the above-mentioned acrylic dispersant. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, and particularly oily dispersants such as polyurethanes, polycarboxylates represented by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, esters of hydroxyl-containing polycarboxylic acids and modified products thereof, or amides or salts thereof formed by reaction of polyesters having free (free) carboxyl groups with poly (lower alkylene imine); water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinyl pyrrolidone; a polyester; a modified polyacrylate; ethylene oxide/propylene oxide adduct, phosphate ester, and the like. As a commercial product of the above resin type dispersant, for example, a cationic resin dispersant is available under a trade name of BYK chemical: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, and DISPER BYK-184; trade name of BASF (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 name of Lubrizol (lubriun) corporation: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; trade name of Chuanjian refining company: HINACT T-6000, HINACT T-7000, HINACT T-8000; trade name of ajinomoto corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; trade name of Kyoeisha chemical Co: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc. The resin type pigment dispersants other than the above-mentioned acrylic dispersant may be used alone or in combination of two or more kinds, or may be used in combination with the acrylic dispersant.
In the case where the colored photosensitive resin composition further contains a pigment dispersant, the content thereof may be 1 part by weight or less, more preferably 0.05 part by weight or more and 0.5 part by weight or less, per 1 part by weight of the colorant contained together. When the amount of the pigment dispersant used is within the above range, a pigment in a uniformly dispersed state can be obtained.
Photopolymerizable compound
The photopolymerizable compound is not particularly limited in the present invention as long as it can be polymerized by irradiation with light via an active radical generated from a photopolymerization initiator, an acid, or the like, and depending on the number of functional groups, a monofunctional, difunctional, trifunctional, or higher polyfunctional polymerizable compound may be mentioned.
Specific examples of the monofunctional polymerizable compound include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone.
Specific examples of the bifunctional polymerizable compound include 1, 6-hexanediol (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, butanediol dimethacrylate, hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate and the like.
Specific examples of the trifunctional or higher polyfunctional polymerizable compound include trifunctional polymerizable compounds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, glycerol propoxylated triacrylate, isocyanurate triacrylate, and the like; tetrafunctional polymerizable compounds such as pentaerythritol tetra (meth) acrylate and dimethylolpropane tetra (meth) acrylate; and pentafunctional or higher polymerizable compounds such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
Among these, the photopolymerizable compounds may be used singly or in combination of two or more, specifically, polyfunctional polymerizable compounds having two or more functionalities may be preferably used, and polyfunctional polymerizable compounds having five or more functionalities may be preferably used, but the photopolymerizable compounds are not limited thereto.
The content of the photopolymerizable compound may be 5 to 50 parts by weight, preferably 7 to 45 parts by weight, based on 100 parts by weight of the total solid content in the colored photosensitive resin composition containing the photopolymerizable compound. When the content of the photopolymerizable compound is in the above range, there is an advantage that the strength and smoothness of the pixel portion can be improved.
Solvent(s)
The solvent of the present invention may be used without any particular limitation as long as it is effective in dispersing or dissolving the other constituent components contained together, and for example, ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, or the like can be preferably used.
Examples of the ethers include tetrahydrofuran, tetrahydropyran, and 1, 4-bis
Alkane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, propylene glycolMonoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, anisole, phenetole, methyl anisole, and the like.
Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene, and the like.
Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-methyl-2-pentanone, cyclopentanone, and cyclohexanone.
Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, and the like.
Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxopropionate, ethyl 3-oxopropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, methyl 2-methoxypropionate, ethyl 2-oxopropionate, ethyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl acetoacetate, ethyl oxyacetate, methyl methoxyacetate, ethyl lactate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl propionate, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxo-2-methylpropionate, ethyl 2-oxo-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ -butyrolactone, etc.
Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide.
Examples of the other solvent include N-methylpyrrolidone and dimethylsulfoxide.
The above solvents may be used singly or in combination of two or more, and among them, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate or propylene glycol methyl ether may be preferably used, and the content of the above solvents may be 10 to 90 parts by weight based on 100 parts by weight of the entire colored photosensitive resin composition containing the same. When the content of the solvent is within the above range, the flatness is good when the colored photosensitive resin composition is applied, and the color density is sufficient when the color filter is formed, so that there is an advantage that the display characteristics can be improved.
Additive agent
The colored photosensitive resin composition may contain additives such as a defoaming agent, a surfactant, a thermal crosslinking agent, a thickener, and an antioxidant, as necessary, in addition to the above components, to improve the performance.
As the surfactant, various surfactants such as a fluorine-containing surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used as a component capable of improving the adhesion between the substrate and the colored photosensitive resin composition. They may be used alone or in combination of two or more.
Specific examples of the fluorosurfactant include MAGAFAC F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, and F781 (trade name, product of DIC corporation); FLUORAD FC430, FC431 and FC171 (trade name, product of Sumitomo 3M Co., Ltd.); SURLON S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (trade name, manufactured by Asahi glass Co., Ltd.); SOLSPERSE 20000 (trade name, product of LUOBRONG Japan, Ltd.), and the like.
Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylated or propoxylated compounds thereof (for example, propoxylated glycerin or ethoxylated glycerin); polyoxyethylene lauryl ethers such as PLURONIC L10, L31, L61, L62, 10R5, 17R2 and 25R2 and TETRONIC 304, 701, 704, 901, 904 and 150R1 (trade names, basf products), polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, and the like.
Specific examples of the cationic surfactant include phthalocyanine-modified compounds such as EFKA-745 (trade name, product of Senseik Co., Ltd.), organosiloxane polymers such as KP341 (trade name, product of shin-Etsu chemical Co., Ltd.); (meth) acrylic (co) polymers such as POLYFLOW Nos. 75, 90 and 95 (trade name, product of Kyoeisha chemical Co., Ltd.), W001 (trade name, product of Yunke Co., Ltd.), and the like.
Specific examples of the anionic surfactant include W004, W005, and W017 (trade name, product of seikagaku corporation).
Specific examples of the SILICONE surfactant include TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (trade names, products of Dow Corning Toray Co., Ltd.), TSF-4440, 4300, 4445, 4460, and 4452 (trade names, products of Mexico high-tech materials Co., Ltd.), KP341, KF6001, and KF6002 (trade names, products of shin chemical Co., Ltd.), BYK307, 323, and 330 (trade names, Bikk chemical Co., Ltd.), and the like.
The thermal crosslinking agent is a component capable of smoothly proceeding a crosslinking reaction by UV irradiation and heat treatment when a coating film is formed from the colored photosensitive resin composition, and improving heat resistance. For example, polyacrylate resins, epoxy resins, phenol resins, melamine resins, organic acids, amine compounds, anhydrous compounds, and the like can be given.
The thickener has an advantage of improving adhesion to inorganic substances that can be used as a base material, for example, silicon compounds such as silicon, silicon oxide, and silicon nitride, and metals such as gold, copper, and aluminum, and improving the ability to adjust the taper angle with respect to the base material. For example, a silane coupling agent or a thiol compound can be mentioned, and a silane coupling agent can be preferably used.
The kind of the silane coupling agent is not particularly limited, and specific examples thereof include gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrialkoxysilane, gamma-glycidoxypropylalkyldialkoxysilane, gamma-methacryloxypropyltrialkoxysilane, gamma-methacryloxypropylalkyldialkoxysilanes, gamma-chloropropyltrialkoxysilanes, gamma-mercaptopropyltrialkoxysilanes, beta- (3, 4-epoxycyclohexyl) ethyltrialkoxysilanes, vinyltrialkoxysilanes and the like, preferably gamma-glycidoxypropyltrialkoxysilanes or gamma-methacryloxypropyltrialkoxysilanes, more preferably gamma-glycidoxypropyltrialkoxysilanes. They may be used alone or in combination of two or more.
Examples of the antioxidant generally include 2-tert-butylphenol, 2, 6-di-tert-butylphenol, 2, 4-di-tert-butylphenol, 2-sec-butylphenol, 2, 6-di-sec-butylphenol, 2, 4-di-sec-butylphenol, 2-isopropylphenol, 2, 6-diisopropylphenol, 2, 4-diisopropylphenol, 2-tert-octylphenol, 2, 6-di-tert-octylphenol, 2, 4-di-tert-octylphenol, 2-cyclopentylphenol, 2, 6-dicyclopentylphenol, 2, 4-dicyclopentylphenol, 2-tert-butyl-p-cresol, 2, 6-di-tert-pentylphenol, 2, 4-di-tert-pentylphenol, 2, 6-di-tert-pentylphenol, 6-tert-butyl-o-cresol, 2, 6-di-tert-dodecylphenol, 2, 4-di-tert-dodecylphenol, 2-sec-butyl-p-cresol, 2, 6-di-tert-octylphenol, 2, 4-di-tert-octylphenol, 6-sec-butyl-o-cresol, 2-tert-octyl-p-cresol, 2-tert-dodecyl-p-cresol, 2-tert-butyl-6-isopropylphenol, 6-tert-octyl-o-cresol, 6-tert-dodecyl-o-cresol, 4' -butylidenebis (3-methyl-6-tert-butylphenol), octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4 '-butylidenebis (6-tetra-butyl-3-methylphenol), 4' -thio-bis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], pentaerythritol-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, methyl-ethyl-propyl-ethyl-methyl-propyl-ethyl-propyl-butyl-4-hydroxy benzyl) benzene, ethyl-butyl-propyl-ethyl-propyl-4, 4-butyl-hydroxy benzyl-propyl-butyl-4, propyl-butyl-propyl-4, propyl-butyl-4, propyl-phenyl, propyl-butyl-phenyl, propyl-phenyl, and propyl-phenyl, 2, 6-di-tert-butyl-4-ethylphenol, 2 ' -methylenebis (4-methyl-6-tert-butylphenol), 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, 5-tris (4-hydroxybenzyl) benzene, tetrakis [ methylene-3- (3,5 ' -di-tert-butyl-4 ' -hydroxyphenyl propionate) ] methane, etc., and preferably, the antioxidant represented by the following chemical formula 8 can be used, and one or two or more of them can be used.
[ chemical formula 8]
(in the above-mentioned chemical formula 8,
R1、R2、R3、R4and R5Each independently represents a linear or cyclic alkyl group having 1 to 10 carbon atoms or hydrogen. )
The method for producing the colored photosensitive resin composition of the present invention can be produced by any method generally used in the art without limitation, and can be produced, for example, by the following method. The colorant is mixed with a solvent in advance and dispersed by a bead mill or the like to the extent that the average particle diameter of the coloring material becomes 0.2 μm or less. In this case, a pigment dispersant may be used as needed, and a part or the whole of the alkali-soluble resin may be blended. The dispersion obtained (hereinafter, also referred to as a "slip") is further added with an excess of the alkali-soluble resin, the photopolymerizable compound, the photopolymerization initiator, the additive, and other components used as needed so as to have a predetermined concentration, and a solvent is added as needed to be mixed therewith, thereby obtaining the desired colored photosensitive resin composition.
< color filter >
The color filter according to another aspect of the present invention, which includes the cured product of the colored photosensitive resin composition, has an advantage that it can form a pattern in the form of a straight slope after a post-baking step in a manufacturing process, thereby preventing problems in the manufacturing process and preventing holes (holes) from being formed in the pattern.
The color filter of the present invention can be manufactured by a manufacturing method generally used in the art without any particular limitation, and an example will be described with reference to fig. 1 to 3, which will be described below.
In order to produce a color filter using the colored photosensitive resin composition of the present invention, it is necessary to form a colored pattern, and for this purpose, the colored photosensitive resin composition is subjected to a pattern treatment. Specifically, referring to fig. 1, a color layer 11 formed of the colored photosensitive resin composition of the present invention is formed on a substrate 10. In this case, the type of the substrate 10 is not particularly limited, and may be a substrate of a color filter itself or a portion where the color filter is located in a display device or the like. The substrate 10 may be a glass plate, a silicon wafer, a plastic plate such as polyether Sulfone (PES) or Polycarbonate (PC), or the like. That is, the substrate 10 may be a silicon (Si), silicon oxide (SiOx), or glass substrate, or may be a polymer substrate. In order to form the color layer 11 made of the colored photosensitive resin composition on the substrate 10, for example, the colored photosensitive resin composition diluted with a solvent is applied to the substrate by a coating method such as spin coating, slot coating, roll coating, spraying, or ink jet method, and then a volatile component such as a solvent is volatilized. Thereby, the color layer 11 made of the colored photosensitive resin composition is formed, and the color layer 11 is made of the solid content of the colored photosensitive resin composition and contains almost no volatile component. The thickness of the film surface is determined by coating conditions such as viscosity of the composition, concentration of solid content, and coating speed, and when the composition of the present invention is used, the color layer 11 having a thickness of 0.5 to 5 μm can be obtained.
Next, referring to fig. 2, the color layer 11 formed of the colored photosensitive resin composition on the substrate 10 is exposed to light 30 (exposure). For exposure, for example, the color layer 11 is irradiated with light 30 in a predetermined pattern through a photomask 20. In this case, the light 30 is generally ultraviolet light such as g-line (wavelength: 436nm), h-line, i-line (wavelength: 365nm), or the like. Light 30 passes in accordance with the pattern of photomask 20. The photomask 20 provides a light-shielding layer that shields light in a predetermined pattern on the surface of the glass plate. The light 30 is blocked by the light blocking layer. The portion of the glass plate not provided with the light shielding layer is a light transmitting portion through which light is transmitted. The color layer 11 is exposed to light according to the pattern of the light-transmitting portion. The irradiation amount of the light 30 is appropriately selected according to the colored photosensitive resin composition to be used.
The portion irradiated with the light 30 has a significantly smaller solubility than the portion not irradiated with the light 30, and the difference in solubility between the two portions is maximized, so that the developing operation is performed using such a difference. For development, for example, the colored photosensitive resin composition layer after exposure is immersed in a developer. As the developer, an aqueous solution of an alkali compound such as sodium carbonate, sodium hydroxide, potassium carbonate, tetramethylammonium hydroxide, or the like is used. Referring to fig. 3, by such development, the light 30 non-irradiated region of the color layer 11 formed on the substrate 10, which is not irradiated with the light 30, is removed. On the other hand, the light 30 irradiated region irradiated with the light 30 remains to constitute the colored pattern 11R. After development, the above layer is usually washed with water and dried to obtain a predetermined colored pattern 11R. After drying, heat treatment may be carried out. The colored pattern 11R formed by the heat treatment is cured, and the mechanical strength thereof is improved. Since the mechanical strength of the colored pattern 11R can be improved by the heat treatment in this way, it is preferable to use a colored photosensitive composition containing a curing agent. The heating temperature is usually 180 ℃ or higher, preferably 200 to 250 ℃.
< image display device >
An image display device according to still another aspect of the present invention includes the color filter, and thus has an advantage of reducing the occurrence of defects because no problem occurs in the manufacturing process. The image display device may be, for example, a Liquid Crystal Display (LCD), an organic EL display (organic EL display), a liquid crystal projector, a display device for a game machine, a display device for a mobile terminal such as a mobile phone, a display device for a digital camera, a display device for a car navigation, or the like, and is particularly suitable for a color display device.
The image display device may include other structures that can be included in a general image display device such as a light emitting device such as a light source, a light guide plate, a liquid crystal display portion including the color filter of the present invention, and the like, and the present invention is not limited thereto.
Hereinafter, preferred embodiments are provided to help understanding of the present invention, and it is obvious to those skilled in the art that the following embodiments are merely illustrative of the present invention, and various changes and modifications can be made within the scope and technical spirit of the present invention, and such changes and modifications also fall within the scope of the appended claims. In the following examples and comparative examples, "%" and "part(s)" representing the content are based on weight unless otherwise specified.
Examples and comparative examples
The colored photosensitive resin compositions were prepared by mixing the components and the contents as shown in table 1 below.
[ Table 1]
[ chemical formula 9]
[ chemical formula 10]
[ chemical formula 11]
[ chemical formula 12]
[ chemical formula 13]
Preparation example: manufacture of color filters
Each of the colored photosensitive resin compositions produced in the examples and comparative examples was coated on a glass substrate by a spin coating method, and then placed on a hot plate and maintained at a temperature of 100 ℃ for 3 minutes to form a thin film. Next, a test photomask having a line/space pattern of 1 to 50 μm was placed on the film, and ultraviolet light was irradiated with the test photomask at a distance of 100 μm from the test photomask. In this case, as the ultraviolet light source, a 1KW high-pressure mercury lamp including all the g, h and i lines was used at a dose of 50mJ/cm2The illumination of (2) is performed without using a special optical filter. The ultraviolet-irradiated film was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 1 minute to be developed. The thin film-coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220 ℃ for 30 minutes, thereby manufacturing a color filter. The film thickness of the color filter produced above was 2.0. mu.m.
Experimental example 1 Pattern slope (taper) morphology
The morphology of the slope after the 220 ℃ heating step in the above production example was measured by a Scanning Electron Microscope (SEM), and the results were judged as shown in fig. 4 and shown in table 2 below.
Experimental example 2 evaluation of Pattern line Width (sensitivity)
The line width of the pattern formed in the above manufacturing example was measured using a Scanning Electron Microscope (SEM). When the line width of the pattern was measured as the line width (100 μm) of the photomask or more, it was evaluated that the sensitivity of the colored photosensitive resin composition was improved and the line width was enlarged. At this time, the measured line width (μm) is shown in table 2 below.
[ Table 2]
Referring to table 2 above, it was confirmed that the color filters produced using the colored photosensitive resin compositions of examples 1 to 4 satisfying all the conditions of the present invention have excellent sensitivity and can produce a pattern in a positive slope form as compared with comparative examples 1 to 4 not satisfying at least one of the conditions of the present invention.
Specifically, the colored photosensitive resin compositions of comparative examples 1 and 3, which did not use the photopolymerization initiator disclosed in the present invention, could form a positive slope, but were found to have a line width of 100 μm or less, and thus were found to have poor sensitivity; the colored photosensitive resin compositions of comparative examples 2 and 4, which did not use the alkali-soluble resin disclosed in the present invention, had a line width of 100 μm or more and sufficient sensitivity, but had a problem of formation of a reverse slope.
Claims (11)
1. A colored photosensitive resin composition characterized by comprising,
comprising a non-reactive alkali-soluble resin and a photopolymerization initiator A,
the non-reactive alkali-soluble resin comprises a repeating unit derived from an N-phenylmaleimide monomer and does not contain an epoxy group or a reactive unsaturated double bond in the molecule,
the photopolymerization initiator a contains a photopolymerization initiator a1 having two oxime groups in one molecule.
2. The colored photosensitive resin composition according to claim 1, wherein the glass transition temperature Tg of the non-reactive alkali-soluble resin is 0 ℃ or lower.
3. The colored photosensitive resin composition according to claim 2, wherein the non-reactive alkali-soluble resin comprises 10 to 50% by weight of repeating units derived from a compound having a glass transition temperature of 0 ℃ or lower.
4. The colored photosensitive resin composition according to claim 3, wherein the compound comprises one or more selected from the group consisting of ethyl acrylate, n-butyl acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl acrylate, and lauryl (meth) acrylate.
5. The colored photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the non-reactive alkali-soluble resin is 3,000 to 12,000.
6. The colored photosensitive resin composition according to claim 1, wherein the content of the non-reactive alkali-soluble resin is 10 to 80 parts by weight based on 100 parts by weight of the entire solid content in the colored photosensitive resin composition containing the same.
7. The colored photosensitive resin composition according to claim 1, wherein the photopolymerization initiator a1 has a molecular weight of 400 to 750.
8. The colored photosensitive resin composition according to claim 1, further comprising at least one selected from the group consisting of a colorant, a photopolymerizable compound, a photopolymerization initiator a2 other than the photopolymerization initiator a1, a solvent, and an additive.
9. The colored photosensitive resin composition according to claim 1, wherein the acid value of the non-reactive alkali-soluble resin is 20 to 200 mgKOH/g.
10. A color filter comprising the colored photosensitive resin composition according to any one of claims 1 to 9.
11. An image display device comprising the color filter according to claim 10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020180032424A KR102335614B1 (en) | 2018-03-21 | 2018-03-21 | Colored photosensitive resin composition, color filter and image display device using the same |
| KR10-2018-0032424 | 2018-03-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110297393A CN110297393A (en) | 2019-10-01 |
| CN110297393B true CN110297393B (en) | 2022-02-11 |
Family
ID=68026406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910195354.9A Active CN110297393B (en) | 2018-03-21 | 2019-03-14 | Colored photosensitive resin composition, color filter comprising same, and image display device |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6763990B2 (en) |
| KR (1) | KR102335614B1 (en) |
| CN (1) | CN110297393B (en) |
| TW (1) | TWI691791B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2022270358A1 (en) | 2021-06-25 | 2022-12-29 | ||
| KR102352657B1 (en) * | 2021-07-19 | 2022-01-18 | 동우 화인켐 주식회사 | Antireflection Film and Organic Light Emitting Display Device |
| KR102408709B1 (en) * | 2021-07-23 | 2022-06-14 | 동우 화인켐 주식회사 | Antireflection Film and Organic Light Emitting Display Device |
| KR102408710B1 (en) * | 2021-07-23 | 2022-06-14 | 동우 화인켐 주식회사 | Antireflection Film and Organic Light Emitting Display Device |
Family Cites Families (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3860170B2 (en) * | 2001-06-11 | 2006-12-20 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Photoinitiators of oxime esters with combined structures |
| JP2005215378A (en) * | 2004-01-30 | 2005-08-11 | Toyo Ink Mfg Co Ltd | Photosensitive colored composition and color filter |
| KR100875269B1 (en) | 2007-08-07 | 2008-12-22 | 제일모직주식회사 | Photosensitive resin composition for color filter and color filter using same |
| WO2009131189A1 (en) * | 2008-04-25 | 2009-10-29 | 三菱化学株式会社 | Ketoxime ester compound and use thereof |
| KR101082489B1 (en) * | 2008-11-05 | 2011-11-11 | 주식회사 엘지화학 | Photo-iniciative polymerizer comprising oxime ester with unsaturated double bonds and photosensative resin composition having the same |
| JP5760374B2 (en) * | 2009-10-23 | 2015-08-12 | 三菱化学株式会社 | Ketoxime ester compounds and uses thereof |
| TWI546574B (en) * | 2011-06-01 | 2016-08-21 | Jsr股份有限公司 | Coloring composition, color filter and display element |
| KR101989198B1 (en) * | 2013-03-28 | 2019-06-13 | 동우 화인켐 주식회사 | A colored photosensitive resin composition and color filter using the same |
| KR20150107491A (en) * | 2014-03-14 | 2015-09-23 | 동우 화인켐 주식회사 | A colored photosensitive resin composition |
| CN103833872B (en) * | 2014-03-18 | 2016-04-06 | 常州强力先端电子材料有限公司 | A kind of two oxime ester lightlike initiating agent and its preparation method and application |
| CN103819583B (en) * | 2014-03-18 | 2016-05-18 | 常州强力电子新材料股份有限公司 | A kind of containing two oxime ester lightlike initiating agents of nitro and its preparation method and application |
| CN104910053B (en) * | 2014-06-09 | 2017-09-12 | 北京英力科技发展有限公司 | Asymmetric two oxime ester compound and its manufacture method and application |
| CN104076606B (en) * | 2014-07-15 | 2019-12-03 | 常州强力电子新材料股份有限公司 | A kind of photosensitive composite and its application containing oxime ester lightlike initiating agent |
| KR101963931B1 (en) * | 2014-12-02 | 2019-04-01 | 동우 화인켐 주식회사 | Black photosensitive resin composition, black matrix and image display device comprising thereof |
| CN105700293A (en) * | 2014-12-12 | 2016-06-22 | 东友精细化工有限公司 | Black photosensitive resin composition, black array and image display device comprising the same |
| KR102001710B1 (en) * | 2015-03-12 | 2019-07-18 | 동우 화인켐 주식회사 | Colored photosensitive resin composition |
| KR20160109834A (en) * | 2015-03-13 | 2016-09-21 | 동우 화인켐 주식회사 | Colored photosensitive resin composition |
| KR20170065111A (en) * | 2015-12-03 | 2017-06-13 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter and image display device produced using the same |
| KR20170082312A (en) * | 2016-01-06 | 2017-07-14 | 동우 화인켐 주식회사 | Colored photosensitive resin composition and color filter using the same |
| CN107522633B (en) * | 2016-06-21 | 2019-12-13 | 常州强力电子新材料股份有限公司 | Fluorenoxime ester photoinitiator |
| KR20180007808A (en) * | 2016-07-14 | 2018-01-24 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter and image display device produced using the same |
| JP2018009132A (en) * | 2016-07-15 | 2018-01-18 | Jsr株式会社 | Colored composition, colored cured film and method for forming the same, and display element |
| KR102560329B1 (en) * | 2016-08-01 | 2023-07-26 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter, and image display apparatus comprising the same |
| CN109666088A (en) * | 2017-10-16 | 2019-04-23 | 北京英力科技发展有限公司 | A kind of diketone oxime ester compound and its manufacturing method and application |
-
2018
- 2018-03-21 KR KR1020180032424A patent/KR102335614B1/en active IP Right Grant
-
2019
- 2019-02-26 TW TW108106468A patent/TWI691791B/en active
- 2019-03-05 JP JP2019039273A patent/JP6763990B2/en active Active
- 2019-03-14 CN CN201910195354.9A patent/CN110297393B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190110682A (en) | 2019-10-01 |
| JP6763990B2 (en) | 2020-09-30 |
| JP2019168679A (en) | 2019-10-03 |
| TW201940972A (en) | 2019-10-16 |
| TWI691791B (en) | 2020-04-21 |
| CN110297393A (en) | 2019-10-01 |
| KR102335614B1 (en) | 2021-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110297393B (en) | Colored photosensitive resin composition, color filter comprising same, and image display device | |
| JP4788485B2 (en) | Colored photosensitive resin composition | |
| KR101047703B1 (en) | Colored photosensitive resin composition and color filter | |
| CN104950600B (en) | Method of manufacturing black column spacer, black column spacer and color filter | |
| KR20070117469A (en) | Colored photosensitive resin composition | |
| KR20150055417A (en) | Colored Photosensitive Resin Composition | |
| KR20120019039A (en) | Colored photosensitive resin composition, color filter and liquid crystal display device having the same | |
| TWI697736B (en) | Black photosensitive resin composition and column spacer comprising the same | |
| KR101526678B1 (en) | Colored photosensitive resin composition, color filter and liquid crystal display having the same | |
| CN111752103B (en) | Red photosensitive resin composition and color filter comprising same | |
| KR20160115438A (en) | Colored photosensitive resin composition | |
| JP7178301B2 (en) | Colored photosensitive resin composition, color filter and image display device manufactured using the same | |
| KR101989198B1 (en) | A colored photosensitive resin composition and color filter using the same | |
| CN108663904B (en) | Colored photosensitive resin composition, color filter and display device | |
| KR101566034B1 (en) | Red colored photosensitive resin composition color filter and liquid crystal display device having the same | |
| KR20140145333A (en) | A colored photosensitive resin composition and color filter comprising the same | |
| KR20150106665A (en) | A colored photosensitive resin composition | |
| TWI766147B (en) | Colored photosensitive resin composition, color filter and image display device using the same | |
| KR102456397B1 (en) | Red colored photosensitive resin composition and color filter comprising the same | |
| KR20160115338A (en) | Colored photosensitive resin composition | |
| KR20150072084A (en) | Colored Photosensitive Resin Composition and Color Filter Comprising the Same | |
| KR101401488B1 (en) | Colored photosensitive resin composition, and color filter and liquid crystal display device prepared by using the same | |
| KR20100094811A (en) | Colored photosensitive resin composition, color filter and liquid crystal display device prepared by using the same | |
| KR101930956B1 (en) | A colored photosensitive resin composition, color filter and liquid crystal display device having the same | |
| KR20160115177A (en) | A colored photosensitive resin comopsition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |