WO2004057380A1 - カラーフィルター用感光性着色組成物、カラーフィルター及びその製造方法 - Google Patents
カラーフィルター用感光性着色組成物、カラーフィルター及びその製造方法 Download PDFInfo
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- WO2004057380A1 WO2004057380A1 PCT/JP2003/015293 JP0315293W WO2004057380A1 WO 2004057380 A1 WO2004057380 A1 WO 2004057380A1 JP 0315293 W JP0315293 W JP 0315293W WO 2004057380 A1 WO2004057380 A1 WO 2004057380A1
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
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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
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
Definitions
- the present invention relates to a photosensitive colored composition useful for producing a color filter used for a color liquid crystal display, a color video camera, an image scanner, etc., a black matrix, a photospacer for liquid crystal, a TFT array, and the like. More specifically, after forming a coating film, it is possible to form an image containing a coloring agent such as a pigment or dye by exposure to ultraviolet light and development with a dilute alkaline aqueous solution, and is excellent in ultraviolet curability, compatibility and developability for liquid color filters.
- a coloring composition is also relates to a method for producing a color filter and a color filter using the photosensitive coloring composition for a color filter. Background art
- the color filter consists of three primary colors of pixels arranged in a triangular, mosaic, and stripe arrangement on the surface of a transparent substrate such as glass. Pixels of a color filter for a charge coupled device (CCD) have a fine shape with a width of several m to several tens m. The pixels of a color filter for a liquid crystal display device (LCD) have a width of several tens of meters; about 200 to 200 mm, and need to be arranged in a predetermined order for each hue.
- CCD charge coupled device
- a method for producing a color filter includes a photosensitive colored composition in which a coloring agent such as a pigment is dispersed in a photosensitive composition that can be developed with an organic solvent or an aqueous alkali solution.
- a method is used in which coating on a glass substrate, drying, exposure to ultraviolet light, and pattern formation by development are repeated. Due to recent environmental problems, alkaline development evenings are currently the mainstream.
- Japanese Patent Application Laid-Open No. 2-144502 is used in such a photosensitive coloring composition because of its excellent weather resistance and little color change.
- Japanese Patent Application Laid-Open No. 3-53201 discloses a photosensitive coloring composition comprising a pigment and a polyfunctional acrylate in an acrylic resin.
- these epoxy (meth) acrylate resins have the disadvantage that they are hard, brittle, inflexible, and have large shrinkage during curing.
- these photosensitive coloring compositions are excellent in weather resistance, sufficient resolution cannot be obtained because the epoxy (meth) acrylate itself as a binder does not affect the curing.
- the physical properties of the coated film after curing, particularly, the alkali resistance, solvent resistance, and moisture resistance were insufficient.
- JP-A-6-230212 discloses a photosensitive coloring composition
- a photosensitive coloring composition comprising a photosensitive compound and a pigment in which a double bond is introduced into the side chain of an acryl resin having a hydroxyl group through an isocyanate.
- Such a composition also cures the acrylic resin itself serving as a binder, so that a cured coating film having excellent alkali resistance and solvent resistance can be obtained.
- the photosensitive coloring composition using such an acrylic resin has insufficient sensitivity and resolution and has tackiness even after the solvent is removed, so that the photomask is often stained at the exposure stage. there were.
- Japanese Patent Application Laid-Open No. 8-262221 discloses a photosensitive coloring composition for a color filter containing an unsaturated group-containing acrylic resin as an essential component. There is a problem that the light sensitivity is not always sufficient. Disclosure of Invention ⁇
- the photosensitive coloring composition for a color filter of the present invention containing as a component has high developability and photosensitivity, and it has been found that a color filter obtained by curing the photosensitive coloring composition can solve the above problems, The present invention has been completed.
- R ′ is a residue of an organic compound RH m containing m active hydrogens in one molecule, RH m — i or a group derived from the residue, and R is an organic compound having active hydrogen.
- R 4 to R 13 are hydrogen atoms; C ⁇ C, which has a hydrocarbon group or an unsaturated group.
- Hydrocarbon group, where the unsaturated group is —OCO— IT ⁇ R 2 is hydrogen atom, R 3 is Ku Wakashi hydrogen atoms.
- at least one of R 4 to R 13 has the unsaturated group.
- R 15 is a residue of a polybasic anhydride
- X is —C ⁇ OH, —OPO (OH) a (OR) b or — OS ⁇ 3 R
- N is an integer of 1 or more, the number is 2 to 50 in the overall molecular structure units
- n represents the number
- p is X Gar OPO (OH) a (OR) b or - if the OS 0 3 R 0 And when X is -C ⁇ OH, it is an integer of 1 or more.
- a photosensitive resin for a color filter comprising a curable resin composition containing a polyether compound represented by the formula, a coloring agent, and a curable resin and / or an ethylenically unsaturated compound added as needed.
- a coloring composition is provided.
- the polyether compound has the following formula (4A) having a plurality of (meth) acryloyl groups and one or more carboxyl groups in one molecule:
- R 'organic compounds RH m residues containing m or more active hydrogens in one molecule - RH m - or a group derived from the residues, R represents an active hydrogen A residue obtained by removing active hydrogen from an organic compound having m, m is 1 to 30, R 4 to R 12 are a hydrogen atom, and C ⁇ d.
- —OC ——CR 3 C RiR 2 R ⁇ ⁇ 2 is a hydrogen atom, R 3 is a hydrogen atom or a methyl group, Y is one (CH 2 ) nl — and nl is 1 to 6 or a part of hydrogen constituting them is replaced by methyl group, ethyl group, propyl group or the following structural formula
- n2 is .1 ⁇ 10 either, R 15 is the residue of polybasic acid anhydride occurs by ring-opening, n is an integer of 1 or more, the molecular structural units n represents the number The total number is 2-50]
- the present invention provides the first photosensitive coloring composition for a color filter of the present invention represented by the formula:
- the polybasic anhydride is tetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride.
- the first or second photosensitive color composition for color filters of the present invention which is at least one selected from the group consisting of acid, hexahydrofluoric anhydride, and 4-methyltetrahydrofluoric anhydride, is provided. .
- R 1 and R 2 are a hydrogen atom
- R 3 is a hydrogen atom or a methyl group
- R 4 to R 12 are each a hydrogen atom, a methyl group, an ethyl group, a propyl group
- Y is one (CH 2 ) nl —where nl is 1 to 6 or a part of hydrogen constituting them is replaced by methyl, ethyl or propyl group, or n2 is 1 to 10 in any of the following structural formulas Stuff. >
- R ′ ′ is a residue of a carboxylic acid, an alcohol, a phenol, an amine, a thiol, or a silanol—! THm-i or a group derived from the residue
- R 1 and R 2 is a hydrogen atom
- R 3 is a hydrogen atom or a methyl group
- R 4 to R 12 are each a hydrogen atom, a methyl group, an ethyl group, a propyl group
- Y is the same as in the formula (2A)
- n is 2 ⁇ 50>
- R 15 is a residue of a polybasic acid anhydride
- R ′ ′′ ′ is _R * H m — or a group derived from the residue>
- the first photosensitive color composition for a color filter of the present invention which is a polyester compound represented by the formula:
- the light-sensitive coloring composition for a color filter according to any one of the first to fourth aspects of the present invention, wherein the organic compound having m active hydrogens in one molecule is trimethylolpropane. Provided.
- the color filter according to the fourth or fifth aspect of the present invention wherein the compound represented by the formula (2A) is 3,4-epoxycyclohexylmethyl (meth) acrylate.
- a single-use photosensitive coloring composition is provided.
- a seventh aspect of the present invention is that the curable resin is a (meth) acrylic acid-ester (meth) acrylate copolymer having the formula (2A)
- R 1 and R 2 are a hydrogen atom
- R 3 is a hydrogen atom or a methyl group
- R 4 to R 12 are each a hydrogen atom, a methyl group, an ethyl group, a propyl group
- Y is — (CH 2 ) nl — where n 1 is from 1 to 6, in which a part of hydrogen constituting these is replaced by methyl, ethyl, or propyl, or n in any of the following structural formulas 2 is from 1 to 10.
- the first photosensitive color composition for a color filter of the present invention which is a resin obtained by reacting a compound represented by the following formula, is provided.
- RH organic compounds polyether compound having m active hydrogen in one molecule m (where, m is 1 to 30, R is an active hydrogen organic compound having an active hydrogen Residue) and formula (2)
- R 4 to R 13 are a hydrogen atom, a hydrocarbon of (:, to (, or a hydrocarbon having an unsaturated group or a hydrocarbon having an unsaturated group), wherein the unsaturated group is 1—CO—CRS— At least one of R 4 to R 13 is the unsaturated group,! ⁇ To 2 is a hydrogen atom, and R 3 is a hydrogen atom or C 1 to C 3 , including CR′R 2 ; Hydrocarbon>
- R ′ ′ is a residue RHm-i of an organic compound having m active hydrogens in one molecule or a group derived from the residue, and R is an active compound from an organic compound having active hydrogens.
- R 4 to R 13 are hydrogen atoms, Cr ⁇ Cm hydrocarbons, or C! To C having an unsaturated group.
- Equation (4) obtained by reacting any of polybasic acid anhydride, phosphoric acid, ethyl phosphate, getyl phosphate, monoalkyl or dialkyl ester of glucose phosphoric acid, sulfuric acid, methyl sulfate, and ethyl sulfate. Equation (4)
- R ' is a group derived from the residue Kiichi RHm- i or the residues of the organic compound RH m containing m pieces of active hydrogen in one molecule
- R represents an organic compound having an active hydrogen
- M is an integer of 1 to 30
- R 4 to R 13 are hydrogen atoms
- Cr ⁇ d having a hydrocarbon group or an unsaturated group.
- at least one of R 4 to R 13 has the unsaturated group.
- R 15 is a residue of a polybasic acid anhydride
- X is one COO H
- N is an integer of 1 or more, the number of the entire molecule of the structural units n represents the number is. 2 to 5
- p is X Gar OPO (OH) a (OR) b or single ⁇ _S_ ⁇ 3 R In the case of 0, it is an integer of 1 or more when X is one C OOH.
- the first photosensitive color composition for a color filter of the present invention which is a polyether compound represented by the formula:
- the curable resin and / or the ethylenically unsaturated compound to be added as necessary is an epoxy group-containing resin and / or an acid group-containing resin.
- a photosensitive coloring composition is provided.
- the photosensitive coloring composition for a power filter according to any one of the first to ninth aspects of the present invention, wherein the polyether compound is a polyether compound synthesized using a reactive diluent as a solvent.
- the polyether compound reacts the mixed gas containing oxygen with a reaction system.
- the first to ninth photosensitive color compositions for color filters according to the present invention which are polyether compounds synthesized by aerating through the air, are provided.
- a color filter obtained by applying the photosensitive coloring composition for a color filter according to any one of the 1st to 11th aspects of the present invention, followed by curing.
- a step of applying the photosensitive coloring composition according to any one of the first to eleventh aspects of the present invention on a substrate patternwise exposing the photosensitive coloring composition applied on the substrate, Photocuring the photosensitive coloring composition in the exposed portion, developing the photosensitive coloring composition that has been subjected to pattern exposure, and leaving a colored layer in which the photosensitive coloring composition has been photocured on the substrate in a pattern.
- a method for producing a color filter is provided. BRIEF DESCRIPTION OF THE FIGURES
- FIG. 1 is an NMR chart of a polyester compound before addition of a dibasic acid anhydride obtained in Synthesis Example 1 according to the present invention.
- FIG. 2 is an NMR chart of the polyether compound of Synthesis Example 2 used in the photosensitive coloring composition according to the present invention.
- FIG. 3 is a sectional view showing an example of a liquid crystal display device using the color filter according to the present invention.
- the polyether compound represented by the formula (4) having a plurality of polymerizable unsaturated groups and one or more acid groups in one molecule, which is used as a main resin component in the photosensitive coloring composition for a color filter of the present invention. Will be described.
- the polyether compound represented by the formula (4) can also be represented by the following formula (IV). Wear.
- R 15 is a residue of a polybasic acid anhydride
- N in one substituent is an integer of 1 or more
- n of each substituent may be the same or different
- the total of n in the whole molecule is 2 to 50
- p is X PO (OH), (OR) b Is 0 if one OS 0 3 R, when X gar COOH, an integer of 1 or more.
- an organic compound RH m having one or more active hydrogens in one molecule (where m is 1 to 30 and R has active hydrogens) (Residues obtained by removing active hydrogen from organic compounds), and these include carboxylic acids, alcohols, phenols, amines, thiols, and silanols.
- carboxylic acids used at this time include formic acid, acetic acid, propionic acid, butyric acid, fatty acids of animal and vegetable oils, phthalic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, Succinic acid, adipic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid, Diphenyl ether tetracarboxylic acid, diacrylic acid) 3-caprolactic acid, 2- (meth) acryloyl quexyl succinic acid, iroxetyl phthalic acid, 2- (meth) acryloyloxetyl hydrogen hydrogen ester, 2- (meth) acryloyloxypropyl hydrogen
- (meth) acryl indicates both acryl and methacryl.
- alcohols include, for example, aliphatic alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, aromatic alcohols such as benzyl alcohol, ethylene glycol, dimethylene glycol, and triethylene.
- Glycol polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, Recol, neopentyl glycol oxypivalate, cyclohexanol, cyclohexanediol, cyclohexanedimethanol, glyce Phosphorus, diglycerin, polyglycerin, trimethylolpropane, trimethylol luetane, penyu erythri!
- Polyhydric alcohols such as phenol, erythritol, hydrogenated bisphenol 8, hydrogenated bisphenol F, hydrogenated bisphenol S, etc., and other (meth) acrylate monomers having a hydroxyl group.
- 2-Hydroxityl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, etc. can also be used.
- phenols examples include phenol, cresol, catechol, pyrogallol, octaidoquinone, octaidoquinone monomethyl ether, biphenol, bisphenol-8, bisphenol F, bisphenol S, 4,4-dihydroxybenzophenone, phenol resin, And cresol nopolak resin.
- Amines include monomethylamine, dimethylamine, monoethylamine, getylamine, monopropylamine, dipropylamine, monobutylamine, dibutylamine, benzylamine, hexylamine, cyclohexylamine, octylamine, dodecylamine, 4,4-diaminodiphenyldimethane, and isomethane.
- amine toluenediamine, hexamethylenediamine, xylenediamine, ethylenetriamine, triethylenetetramine, ethanolamine and the like.
- thiols examples include methyl mercaptan, ethyl mercaptan, propyl mercaptan, and phenyl mercaptan.
- Other compounds having one or more active hydrogens include silicone compounds having silanol groups, polyvinyl alcohol, partially hydrolyzed polyacetate biel, starch, acrylic polyol resin, styrene aryl alcohol copolymer resin, and the like.
- Styrene-maleic acid copolymer resin alkyd resin, polyester polyol resin, polyester carboxylic acid resin, polycaprolactone polyol resin, polypropylene polyol, polytetramethylene dalicol, polycarbonate polyols and hydroxyl-containing polybutadiene, cellulose, cellulose There are cellulose polymers such as acetate, cellulose acetate butyrate, and hydroxyethyl cellulose. W
- Any compound can be used as long as it has one or more active hydrogens, and they may be used in combination of two or more.
- the polyether compound represented by the formula (3) can also be formed by using water in the raw material as an initiator without using the compound having one or more active hydrogens.
- a catalyst As the catalyst, mention may be made of BF 3, ZnC A l Ch, complexes with a like Lewis acids or their and ethers such as S nC 1 4. Further, a light-powered thione catalyst that generates an acid by irradiation with a sulfonium-based or ionium-based light can also be used. These catalysts are preferably used in an amount of 0.01 to 10% by weight, particularly preferably in a range of 0.1 to 5% by weight, based on the reactants.
- the reaction takes a long time, which is not preferable. On the other hand, use of more than 10% by weight is not preferred because side reactions are likely to occur, and the product is colored or gelled.
- the reaction of carboxylic acids, alcohols, phenols, amines, and thiols having one or more active hydrogens in one molecule with the compound represented by the formula (2) is carried out by the above-mentioned sulfonic acid group, hydroxyl group, etc. It is essential that the epoxy group of the compound represented by the formula (2) be used in a ratio of 2 to 50 chemical equivalents with respect to 1 chemical equivalent of, preferably 3 chemical equivalents or more, particularly 5 chemical equivalents.
- the reaction time is preferably 0.5 to 24 hours, particularly preferably 2 to 5 hours.
- the reaction temperature is preferably from 150 to 100, and particularly preferably from 120 to 50. If the temperature exceeds 100 ° C, gelation is likely to occur and coloring is intense. In order to suppress gelation and coloring, it is effective to use the following solvents.
- the solvent a solvent having no active hydrogen as described in JP-A-4-164921 and JP-A-4-1258617 can be used.
- ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
- aromatic solvents such as benzene, toluene and xylene
- ethers aliphatic hydrocarbons and esters
- acrylate monomers having neither an active hydroxyl group nor an active lipoxyl group can be used in addition to diacetate of ethylene glycol or propylene glycol, methyl ether acetate of ethylene glycol or propylene glycol, and the like.
- the amount of the solvent to be used is 0.2 to 5 times, preferably 0.5 to 3 times the weight of the starting material. If the amount of the solvent is less than 0.2 times the amount of the starting material, the viscosity of the product becomes high, so that it is difficult to remove heat of reaction and the obtained product is colored, which is not preferable. Conversely, if the amount exceeds 5 times, a polyether compound having a plurality of polymerizable unsaturated groups and one or more acid groups in one molecule represented by the above formula (4) simultaneously becomes a photosensitive coloring composition for a color filter. When used as a cured product, the curing speed is slow and the physical properties of the cured product are inferior.
- JP-A-4-1258617 described above discloses that 50 to 100,000 ppm of hydropen quinone, hydroquinone monomethyl ether, methylhydroquinone, p-benzoquinone, phenothiazine and the like are added to the reaction solution.
- the polymerization inhibitor having active hydrogen during the synthesis reacts with the substrate and loses its effect, so that the polyether represented by the formula (4) in the present invention is used.
- 3,4-epoxycyclohexylmethyl (meth) acrylate (manufactured by Daicel Chemical Industries, Ltd., Cycomer A-200, etc.) is preferred.
- reaction of reacting the active hydrogen-containing organic compound R Hm with the epoxy compound represented by the formula (2A) to obtain a polyether compound represented by the formula (3A), or the reaction of the R Hm and the formula (2A) in the reaction to obtain the polyether compounds described by reacting an epoxy compound formula (3) described in 2), also reacted with the R Hm and epoxy ring reacts with the side close to the R 7 of the epoxy ring R 8 may be reacted with a side closer to describe the exemplary embodiment that reacted with the side close to the R 7 in the formula (3 a) or formula (3).
- polyether compound of the formula (3) obtained as described above By reacting the polyether compound of the formula (3) obtained as described above with a polybasic acid anhydride, a plurality of polymerizable unsaturated compounds in one molecule represented by the formula (4) in the present invention are obtained. A polyether compound having a group and one or more acid groups is obtained.
- the polybasic acid anhydride to be reacted is not particularly limited, and any of a saturated polybasic acid anhydride and an unsaturated polybasic acid anhydride, which itself already contains an acid group such as a carboxyl group, etc. Acid anhydrides can also be used.
- polybasic acid anhydrides examples include succinic anhydride, maleic anhydride, fluoric anhydride, nadic anhydride, tetrahydrophthalic anhydride, tetrabromophthalic anhydride, and hexahydrofuran anhydride.
- succinic anhydride phthalic anhydride, tetrahydrophthalic anhydride and methyltetrahydrophthalic anhydride
- succinic anhydride phthalic anhydride, tetrahydrophthalic anhydride and methyltetrahydrophthalic anhydride
- alicyclic polybasic anhydrides are particularly preferred.
- one kind of polybasic acid anhydride may be used alone, or two or more kinds may be used in combination.
- polybasic anhydrides include 3,4,5,6-tetrahydrophthalic anhydride, tetrahydrophthalic anhydride at other hydrogenation positions, 4-methyltetrahydrophthalic anhydride, and 3-methyltetrahydroanhydride.
- phthalic acid, hexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride are used, the resulting polyether compound of the formula (4) has X as -C00H and has the following structural formula. Become.
- R 14 is represented by a hydrogen atom or an alkyl group such as a methyl group.
- X is - 0s0 3
- the acidic sulfuric esters such as sulfuric acid and Echiru sulfate and methyl sulfate, etc. in place of the polybasic acid anhydride (such sulfate) is used.
- reaction with polybasic acid anhydride, phosphoric acid, or sulfuric acid should be performed in the form of a reactive diluent solution without separating the reaction medium used for synthesizing the polyether compound of the formula (3).
- the reaction may be performed by separating the reactive diluent.
- polybasic acid anhydrides are used for converting aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, isopropanol and cyclohexanol, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and petroleum.
- Petroleum-based solvents such as ether and petroleum naphtha, cellosolves such as cellosolve and butyl sorbitol, carbyl such as carbiyl and butyl carbitol], ethyl acetate, butyl acetate, cellosolve acetate, and butyl sorbate acetate Acetates such as acetic acid, butyl carbitol acetate, methyl ethyl ketone, and cyclohexanone. You may dissolve in any ketone etc. and carry out addition reaction.
- a photopolymerizable monomer can be used as a reactive diluent.
- Examples of the photopolymerizable monomer that can be used as the reactive diluent include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and 2- Ethyl hexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyshetyl (meth) acrylate, 2-ethoxyhexyl (meth) acrylate, 2-butoxysethyl ( Monofunctional acrylate compounds such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, and ethyl carbitol (meth) acrylate, ethylene glycol di (meth
- one of these reactive diluents can be used alone, or two or more of them can be used in combination.
- the reaction between the polyether compound of the formula (3) and the polybasic acid anhydride is carried out in the presence of a polymerization inhibitor such as hydroquinone-methquinone under aeration of a mixture containing oxygen at 80 to 12%. It is preferable to carry out at 0 ° C. If the reaction temperature is lower than 80 T, the reaction rate may be slow and the reaction may take a long time. If the reaction temperature exceeds 12 Ot :, the polyfunctional acrylate will undergo thermal polymerization, which may cause gelation during the reaction.
- a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, or an imidazole such as 2-ethyl-4-methylimidazole can be used.
- Compounds and phosphorus compounds such as triphenylphosphine may be added as catalysts.
- the polyester compound which is a main resin component in the photosensitive coloring composition for a color filter of the present invention is, as apparent from the above-mentioned synthesis method, a ring-opening of the polybasic acid anhydride, a phosphoric acid, and a sulfuric acid. Is represented by the following formula (4).
- R ' is RH remaining Kiichi organic compound RH m containing m pieces of active hydrogen in one molecule m - i or a group derived from the residues
- an organic compound R is having an active hydrogen
- M is an integer of 1 to 30
- R 4 to R 13 are a hydrogen atom, a C 1 to C 10 hydrocarbon group, or a C 1 to C 10 hydrocarbon group having an unsaturated group
- the unsaturated group is R 1 and R 2 are a hydrogen atom
- R 3 is Ku Wakashi hydrogen atoms C1 to (: 10 a hydrocarbon group, and, C1 having 1 ⁇ 4 to 1 13 at least Tsu is the unsaturated group ⁇
- R 15 is a polybasic acid anhydride, monoalkyl ester or dialkyl ester such as phosphoric acid and ethyl phosphate, getyl phosphate, or glucose phosphoric acid, or sulfuric acid and ethyl sulfate
- R 15 is
- n is an integer of 1 or more, and the number of structural units in which n represents the number in the entire molecule is required to be 2 to 50, preferably 5 to 50.
- a 20 p is X is -. 0P0 (OH) a ( oR) b or - 0s0 3 a case 0 of R, X is - C00H, is an integer of 1 or more.
- R 15 is a ring-opening residue such as a polybasic acid anhydride, and preferably contains an alicyclic group.
- the acid value (solid content equivalent) of the polyether compound represented by the formula (4) is 5 to 150 (KOHmg / g), usually 5 to 150 (KOHmg / g) in consideration of alkali developability and sensitivity. ), Preferably 25 to 150 (KOHmg / g).
- the acid value is 5 (KOHmg / g) or less, developability with a dilute aqueous alkaline solution is poor.
- the acid value exceeds 300, the water resistance, alkali resistance, and humidification properties of the cured coating film or color filter deteriorate.
- R ′ in the above formula (4) is represented by the activity of the polyvalent compound.
- the structure is the same as RHm-i in the case where hydrogen remains as it is, and m- 1 active hydrogen all reacts when 1 active hydrogen reacts and R 'in formula (4) is removed.
- R ′ ′ represents not only one RHm-i when the active hydrogen contained therein remains as it is, but also m ⁇ 1 one active water when one active hydrogen has reacted.
- the “group derived from the residue” refers to such a case. More specifically, when trimethylolpropane is used as an organic compound containing m active hydrogens in one molecule, the compound of formula (3) shows that R ′ ′ is the residue CH 3 CH 2 C (CH 2 OH) 2 CH 2 O— (the remaining active hydrogens are all unreacted), and one or all of the two active hydrogens contained therein are used as the starting point of the reaction.
- the photosensitive coloring composition for a color filter of the present invention preferably contains the polyether compound represented by the formula (4) in an amount of 15% by weight or more.
- the photosensitive coloring composition for color filling of the present invention is obtained by adding the above-mentioned polyether compound, a coloring agent, and a (meth) acrylic acid- (meth) acrylic acid ester copolymer, which is added as required, to the formula (2) It can be obtained by blending a curable resin such as a resin obtained by adding the compound represented by A), and a Z or ethylenically unsaturated compound.
- a curable resin such as a resin obtained by adding the compound represented by A
- Z or ethylenically unsaturated compound Specific examples of the curable resin include “ACA200” and “Cyclomer Pj” manufactured and sold by Daicel Chemical Industries.
- ethylenically unsaturated compound examples include: ⁇ -potassium lipoxyshetyl (methyl) acrylate, isoponyl (meth) acrylate, octyldecyl (meth) acrylate, ethoxyphenyl (meth) acrylate, diethylene glycol monoethyl ether (meta).
- the polyether compound represented by the formula (4) may be converted into another polymerizable oligomer such as epoxy acrylate, urethane (meth) acrylate, unsaturated polyester / polyester (meth) acrylate and polyether (meth). It may be used in combination with acrylate or these polymers.
- another polymerizable oligomer such as epoxy acrylate, urethane (meth) acrylate, unsaturated polyester / polyester (meth) acrylate and polyether (meth). It may be used in combination with acrylate or these polymers.
- a curable resin and / or an ethylenically unsaturated compound such as a resin obtained by adding the compound represented by the formula (2A) to the (meth) acrylic acid-mono (meth) acrylate copolymer described above are used. If necessary, one or more kinds can be mixed and used at an arbitrary ratio.
- the amount of a curable resin such as a resin obtained by adding a compound represented by the formula (2A) to a (meth) acrylic acid (meth) acrylate copolymer and / or an ethylenically unsaturated compound is used.
- the resin component is used in an amount of 0 to 85% by weight, preferably 10 to 80% by weight, and more preferably 50 to 80% by weight.
- the amount of the curable resin and / or the ethylenically unsaturated compound used exceeds 85% by weight, the effect obtained by using the polyether compound represented by the formula (4) is obtained in the color filter obtained. I can't get it.
- curable resins and ethylenically unsaturated compounds can be synthesized by known methods and can be easily obtained from the market.
- a plurality of polymerizable unsaturated groups and one or more acid group-containing polyether compounds in one molecule are a coloring agent, a curable resin and / or an ethylenically unsaturated compound added as necessary, and an appropriate photoinitiator.
- the photosensitive (photo-curable) coloring composition for a color filter of the present invention is obtained.
- photoinitiator examples include benzophenone, methyl orthobenzoyl benzoate, 4-dimethylaminoethyl benzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), 2,4-getylthioxanthone (Nippon Kayaku Co., Ltd.
- the coloring agents to be incorporated into the photosensitive coloring composition for a color filter of the present invention are four colors of red, green and blue, which are called three primary colors of light, and black of a black matrix portion used as required.
- the coloring agent includes a dye and a pigment, and a pigment is preferable in terms of heat resistance and light resistance.
- examples of such pigments include inorganic pigments such as barium sulfate, zinc white, lead sulfate, titanium oxide, yellow lead, red iron oxide, ultramarine, navy blue, chromium oxide, and carbon black, benzine yellow G, benzine yellow GR, and sole.
- Organic pigments such as First To Orange 3GL, Palkan First Orange GC, Pigment Scarlet 3B, Chokunzigo Maroon, Phthalocyanine Blue, Phthalocyanine Green, Indanthrene Blue, Green Gold, Mariki Light Green Lake, etc. Specifically, the following are exemplified. All are color indexes
- C.I. Color Index pigment
- the pigment used is an organic pigment with excellent transparency. Is preferred.
- the pigment used as a coloring agent should be one in which the primary particles have a particle size of 50% by weight or more and 0.3% or less and 5% by weight or less of primary particles. It is preferable from the viewpoint of transparency and dispersibility. More preferably, all of the primary particles have a particle size of 0.1 m or less, and are sufficiently small with respect to the wavelength of visible light. When the primary particles of 0.3 zm or less are less than 50% by weight of all the particles, or when the primary particles of 1 m or more are more than 5% by weight, the transparency of the photosensitive coloring composition for a color filter is poor. However, it is not particularly suitable for color filters that require transparency.
- the mixing ratio of the coloring agent in the photosensitive coloring composition for a color filter is in the range of 50 to 1,000 parts by weight, preferably 50 to 500 parts by weight, based on 100 parts by weight of the solid content of the photosensitive coloring composition. If the ratio of the coloring agent is less than 50 parts by weight, the characteristics as a filter are improved, but in order to obtain a predetermined optical density, it is necessary to increase the film thickness, which makes fine processing difficult.
- the photosensitive coloring composition for color fills of the present invention is required as other additives. It may contain a thermal polymerization inhibitor, a pigment dispersant, and the like, as appropriate. Further, a thermoplastic resin, a thermosetting resin, and the like can also be blended.
- the pigment dispersant is added as appropriate to improve the dispersibility of the pigment.
- the weight ratio of the pigment dispersant to the pigment is preferably in the range of 0.01 to 0.2, but need not necessarily be limited to this range.
- various surfactants such as cationic surfactants, anionic surfactants and nonionic surfactants, and derivatives of organic dyes are used.
- Such a dispersant is excellent in dispersibility of the pigment and has a large effect of preventing re-aggregation of the pigment after dispersion, so that a color filter having excellent transparency can be obtained.
- Organic dyes used as the parent include azo, phthalocyanine, quinacridone, anthraquinone, perylene, perinone, thioindigo, dioxazine, isoindolinone, quinophthalone, triphenylmethane, and metal complex salts.
- System. Derivatives having substituents on these organic dyes and effective in dispersing the pigment are used.
- the substituent is, for example, a hydroxyl group, a hydroxyl group, a sulfonic acid group, a carbonamide group, a sulfonamide group, or any of the substituents represented by the following general formulas or formulas (18) to (23).
- a derivative having at least one substituent selected from these substituents is used.
- the pigment and the parent organic pigment of the pigment dispersant are usually the same, but need not always be the same.
- R 1 , R 2 hydrogen atom or alkyl group, or heterocycle containing at least nitrogen atom by combining R 1 and R 2 )
- R 1 hydrogen atom, alkyl group or aryl group
- R 2 an alkyl group or aryl group, or a heterocyclic ring containing at least a nitrogen atom by combining R 1 and R 2 )
- A an alkylene group
- R 2 an alkyl group, an alkoxyalkyl group or a cycloalkyl group,
- R 3 a hydrogen atom, a cycloalkyl group, or a heterocyclic ring containing at least a nitrogen atom by combining R 2 and R 3 )
- amino group-containing boractones represented by the following general formula (24) can also be used as a pigment dispersant.
- R an aliphatic, alicyclic, or aromatic hydrocarbon residue, in which the N atom may form a ring together with R, and may have a substituent;
- k an integer of 15.
- R 1 is hydrogen or a methyl group
- R 2 is an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 110 carbon atoms, or is a polypropylene oxnitite or a polyethylene oxnitite, and may have a substituent;
- R 3 an alkylene group having 3 10 carbon atoms which may have a side chain having 15 carbon atoms, wherein n R 3 may be the same or different,
- an amino group-containing compound represented by the following general formula (26) can also be used as a pigment dispersant. That is, a compound represented by the general formula (26) containing, as an essential component, a unit having a functional group capable of undergoing a Michael addition reaction with an amino group at a terminal and having a polyester chain formed by ring opening of the lactone compound represented by the general formula (27). PO shown It is a ester compound.
- X a unit having a functional group capable of undergoing a Michael addition reaction with an amino group at a terminal
- Y a unit having a polyester chain formed by ring-opening of a lactone compound (27);
- R represents an alkyl group having 1 to 20 carbon atoms, or an aromatic group, an OH group, a cyano group, or a halogen.
- R 1 is an alkylene group having 1 to 10 carbon atoms which may be substituted with an aliphatic alkyl group having 1 to 10 carbon atoms.
- a method for producing a color filter using the photosensitive coloring composition for a color filter of the present invention is as follows. First, a coating method such as spray coating, spin coating, or slit coating is applied onto a glass substrate or the like as a transparent substrate. Apply the composition. The dried coating film has a thickness of 1 to 3 m and is exposed to ultraviolet light through a positive or negative mask having a predetermined pattern in a contact or non-contact state.
- the unhardened portion is removed by immersing in an alkali developer or spraying an alkali developer with a spray or the like, and the same operation is repeated thereafter. Further, heating can be performed as necessary to promote polymerization of the photosensitive resin.
- an aqueous solution of sodium carbonate, trialkylammonium hydroxide, caustic soda or the like is used as an alkaline developer.
- Dimethylpentylamine It is also possible to add amines such as triethanolamine, and trialkylammonium halides.
- a water-soluble or alkali-water-soluble resin for example, a water-soluble acrylic resin or a polyvinyl alcohol resin
- Filter 10 separates the three primary colors. Further, the light passes through the transparent substrate 11 and the polarizing plate 12 and is recognized as a color by visual perception. In such a display device, the liquid crystal 6 is sealed in contact with the alignment films 5 and 8 and the sealing material 7, and the direction of the alignment is changed by an electric signal applied between the pixel electrode 4 and the transparent electrode 9. Change.
- each color of the color filter 10 is the same as the pixel electrode 4, and is several millimeters square for a large display, and several tens to several hundreds of micrometers square for a handy display. 10 must be made of a material that can be finely processed.
- the configuration of the color filter of the present invention will be described below. As shown in FIG. 3, as the transparent substrate 11, a glass substrate, a transparent resin plate, a transparent resin film or the like can be applied.
- the color filter 10 is usually located on the transparent substrate 11, and a transparent electrode 9 is generally provided on the color filter 10.
- the color filter 110 includes, for example, a red filter layer R, a green filter layer G, and a blue filter layer B.
- a black or opaque light-shielding layer or an uncolored layer may be provided between R, G, and B.
- the red filter layer R is composed of a polyether compound having a plurality of polymerizable unsaturated groups and one or more acid groups in one molecule, a curable resin added as necessary, and a Z or ethylenically unsaturated compound, a red pigment, It is composed mainly of a pigment dispersant.
- the green filter layer G and the blue filter layer B are also composed mainly of the same polyether compound, a curable resin and / or an ethylenically unsaturated compound, a pigment, and a pigment dispersant added as necessary.
- the role of the polyether compound, the curable resin and the Z- or ethylenically unsaturated compound added as needed is to fix each color pigment on the transparent substrate 11 and, if necessary, to have any shape. It becomes possible to form a pattern, and it becomes a base material when the transparent electrode 9 is formed on the color filter 10.
- Parts means “parts by weight”. Synthesis of various polyethers
- TMP trimethylolpropane
- initiator an organic compound containing active hydrogen R Hm (referred to as initiator in the following table)
- 3,4-epoxycyclohexylmethyl acrylate a compound having the structure of the formula (2) (Cyclomer A-200, manufactured by Daicel Chemical Industries, Ltd.) (Table shows A200.) 2730 parts and toluene (1540 parts) were charged, the liquid temperature was raised to 35 ° C, and then 41 parts of boron trifluoride getyl ether complex was added dropwise in about 3 hours to carry out the reaction.
- Table shows A200.
- the mixture was reacted until the oxysilane oxygen concentration of the mixture became 0.05% or less.
- a mixture of nitrogen and air with an oxygen concentration of 7% was passed through the liquid at 83 ml / min.
- the solid content (120 °) of the obtained compound corresponding to the formula (3) (here, referred to as a polyacrylate compound, but may be referred to as a polymethacrylate compound depending on a raw material used in the following synthesis examples, etc.) C * 1 hour dry residue), viscosity and molecular weight by GPC were as follows.
- the ratio of the absorption intensity of 0.9 ppm of the methyl moiety (C3 ⁇ 4: 3 H) of the trimethylolpropane used as the ring-opening initiator to the intensity of the 1H proton attached to the tertiary carbon on the cyclo ring is 2: 1. It is 0 and it can be confirmed that it matches the theoretical value from the charged mol ratio of 1:15.
- the polyacrylate compound obtained as described above is further added with a dibasic anhydride.
- the tetrahydrofuric anhydride was subjected to an addition reaction as follows.
- the obtained polyether compound of the formula (4) (here, referred to as an acid anhydride-added polyacrylate compound, but in the following synthesis examples, etc., depending on the raw materials used, it may be referred to as an acid anhydride-added polymethacrylate compound).
- the solid content 120 ° C * dried for 1 hour
- viscosity and molecular weight by GPC were as follows.
- the solid content (dried at 120 * 1 hour), viscosity, and molecular weight by GPC of the obtained polyacrylate compound were as follows.
- the acid value is 74K0Hmg / g against the theoretical value of 72K0Hmg / g for this reaction (acid value in terms of solid content: 103 OHmg / g), and the GPC measurement shows that the acid value is low due to tetrahydrophthalic anhydride. It was confirmed that the peak on the molecular side was almost eliminated.
- the solid content (120 ° C * 1 hour drying), viscosity and molecular weight by GPC of the obtained acid anhydride-added polyacrylate compound were as follows.
- the mixture was reacted until the oxysilane oxygen concentration of the mixture became 0.05% or less. Until the reaction was completed, a mixture of nitrogen and air having an oxygen concentration of 7% was passed through the liquid at 50 ml / min to prevent gelation due to radical polymerization during the reaction.
- the solid content (dried at 120 ° C * 1 hour), viscosity and molecular weight by GPC of the obtained polymer acrylate compound were as follows.
- the polyacrylate compound obtained as described above was further subjected to an addition reaction with tetrahydrophthalic anhydride, which is a dibasic acid anhydride, as follows.
- the solid content (dried at 120 ° C. * 1 hour), viscosity, molecular weight by GPC and the like of the obtained polyacrylate compound were as follows. '
- a 2-liter reactor equipped with a stirrer, a temperature controller and a thermometer was charged with acrylic acid (AA) 72 parts and 3,4-epoxycyclohexylmethyl acrylate (Daicel Chemical Industries Cyclomer A-200, manufactured by Co., Ltd.) 910 parts, toluene 165 parts, and hydroquinone monomethyl ether 0.91 part as a polymerization inhibitor were charged, and the liquid temperature was raised to 35 ° C. 13.7 parts of borohydride getyl ether complex was added dropwise in about 3 hours, and the reaction was scheduled to be carried out.However, when the reaction was carried out without passing a mixture of nitrogen and air during the reaction, did.
- the viscosity and molecular weight by GPC of the obtained compound were as follows.
- the reaction is carried out for 10 hours, and the acid value is 48K0Hmg / g compared to the theoretical value of 46K0Hmg / g for this reaction (acid value in terms of solid content: 69K0Hmg / g), and GPC measurement is based on tetrahydrophthalic anhydride. It was confirmed that the peak on the side had almost disappeared.
- an epoxy (meth) acrylate resin in which an epoxy group of an epoxy resin described in JP-A-6-157965 is subjected to a ring-opening reaction with acrylic acid (AA) ⁇ methacrylic acid, and The following synthesis was carried out in order to obtain an acid anhydride-added product.
- the viscosity and molecular weight by GPC of the obtained compound were as follows.
- the reaction is carried out for 10 hours, and the acid value is 33K0Hmg / g against the theoretical value of 32K0Hmg / g for this reaction (acid value in terms of solid content 48K0Hmg / g), and the GPC measurement is based on tetrahydrofluoric anhydride. It was confirmed that the peak on the low molecular side was almost eliminated.
- Acid value * Solid value corrected acid value
- a commercial product obtained by adding 3,4-epoxycyclohexylmethyl acrylate of formula (2A) to a copolymer of methacrylic acid and methyl methacrylate, which is used in the field of resists developed by Alkali Chemical Co., Ltd. Using ACA200 manufactured by Kogyo Co., Ltd., R
- the red resist obtained above is subjected to microfiltration with a pore size of 1 iim, and the solvent is dried on a glass substrate on which a black matrix pattern has already been formed by spin-coating so that the film thickness becomes 1.3 m. Spin coated.
- an aqueous solution of polyvinyl alcohol was spin-coated, dried with water, and exposed using a photomask for pattern formation.
- Color filters were prepared in the same manner as in Examples I to II except that the polyether compound and the monomer (DHPA) were changed.
- the performance of the color filters obtained in Examples and Comparative Examples was evaluated by the following methods. Table 3 shows the evaluation results.
- the coating film obtained in the same manner as in the measurement of the resolution was heated in a hot air circulation dryer at 230 ° C for 60 minutes, and the transmittance of the obtained cured coating film was measured by a spectrophotometer. The measurement was performed using 700 nm light for the red resist, 540 nm for the green resist, and 460 nm for the blue resist using Nihon Spectroscopy.
- the cured coating film obtained in the same way as in the measurement of transmittance is heated in a hot air convection type drying oven at 250 ° C for 60 minutes, and the change in transmittance at a predetermined wavelength before and after heating was measured.
- the evaluation results were represented by ⁇ : 5% or less, ⁇ : 5 to 10%, and X: 10% or more.
- a light-sensitive coloring composition for a color filter which has no tackiness even after removal of a solvent, does not stain a photomask in an exposure step, and has sufficient light sensitivity and resolution. We were able to.
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Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003303281A AU2003303281A1 (en) | 2002-11-29 | 2003-11-28 | Colored photosensitive composition for color filters, color filters, and process for the production thereof |
JP2004562016A JPWO2004057380A1 (ja) | 2002-11-29 | 2003-11-28 | カラーフィルター用感光性着色組成物、カラーフィルター及びその製造方法 |
US10/536,389 US20060257759A1 (en) | 2002-11-29 | 2003-11-28 | Colored photosensitive composition for color filter, color filter, and process for the production thereof |
EP03813718A EP1571469A4 (en) | 2002-11-29 | 2003-11-28 | COLORFUL LIGHT-SENSITIVE COMPOSITION FOR COLOR FILTER, COLOR FILTER AND PROCESS FOR THEIR PRODUCTION |
Applications Claiming Priority (2)
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JP2002-349305 | 2002-11-29 | ||
JP2002349305 | 2002-11-29 |
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WO2004057380A1 true WO2004057380A1 (ja) | 2004-07-08 |
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PCT/JP2003/015293 WO2004057380A1 (ja) | 2002-11-29 | 2003-11-28 | カラーフィルター用感光性着色組成物、カラーフィルター及びその製造方法 |
Country Status (8)
Country | Link |
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US (1) | US20060257759A1 (ja) |
EP (1) | EP1571469A4 (ja) |
JP (1) | JPWO2004057380A1 (ja) |
KR (1) | KR20050086893A (ja) |
CN (1) | CN1717598A (ja) |
AU (1) | AU2003303281A1 (ja) |
TW (1) | TW200500335A (ja) |
WO (1) | WO2004057380A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008165059A (ja) * | 2006-12-28 | 2008-07-17 | Fujifilm Corp | 硬化性組成物、カラーフィルタ及びその製造方法 |
CN101154039B (zh) * | 2006-09-25 | 2012-05-23 | 富士胶片株式会社 | 可固化组合物、滤色器及其制造方法 |
Families Citing this family (7)
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TWI428691B (zh) * | 2006-09-25 | 2014-03-01 | Fujifilm Corp | 硬化組成物、彩色濾光片及其製法 |
JP4855299B2 (ja) * | 2007-02-27 | 2012-01-18 | 富士フイルム株式会社 | 着色感光性組成物、カラーフィルター及びその製造方法 |
JP5024107B2 (ja) * | 2007-03-13 | 2012-09-12 | Jsr株式会社 | 着色層形成用感放射線性組成物、カラーフィルタおよびカラー液晶表示素子 |
JP5339686B2 (ja) * | 2007-03-30 | 2013-11-13 | 富士フイルム株式会社 | 顔料分散組成物、硬化性組成物、並びにカラーフィルタ及びその製造方法 |
JP4890388B2 (ja) * | 2007-08-22 | 2012-03-07 | 富士フイルム株式会社 | 着色感光性組成物、カラーフィルタ及びその製造方法 |
KR101607705B1 (ko) * | 2007-11-22 | 2016-03-30 | 토요잉크Sc홀딩스주식회사 | 컬러 필터용 녹색 착색 조성물, 및 컬러 필터 |
JP6357485B2 (ja) * | 2013-11-28 | 2018-07-11 | 日本化薬株式会社 | 活性エネルギー線硬化型樹脂組成物、及びそれを用いた表示素子用スペーサー及び/またはカラーフィルター保護膜 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0540027A2 (en) * | 1991-10-31 | 1993-05-05 | Daicel Chemical Industries, Ltd. | Compositions, expoxidized compositions, a heat-curable resin composition, an epoxy resin composition, radically polymerized composition, a curable resin composition and a polymer having epoxy groups |
JPH09179296A (ja) * | 1995-12-22 | 1997-07-11 | Mitsubishi Chem Corp | 光重合性組成物 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5882843A (en) * | 1994-11-15 | 1999-03-16 | Hoechst Japan Limited | Photosensitive resin composition for color filter production |
US5650233A (en) * | 1995-01-05 | 1997-07-22 | Daicel Chemical Industries, Ltd. | Photo-setting colored filter composition, a color filter, a process for the preparation thereof, and a curable resin composition |
US20050228162A1 (en) * | 2002-04-04 | 2005-10-13 | Akira Okazaki | Novel polyether compound containing acid group and unsaturated group, process for producing the same, and resin composition |
-
2003
- 2003-11-28 JP JP2004562016A patent/JPWO2004057380A1/ja not_active Ceased
- 2003-11-28 US US10/536,389 patent/US20060257759A1/en not_active Abandoned
- 2003-11-28 KR KR1020057009668A patent/KR20050086893A/ko not_active Application Discontinuation
- 2003-11-28 WO PCT/JP2003/015293 patent/WO2004057380A1/ja not_active Application Discontinuation
- 2003-11-28 EP EP03813718A patent/EP1571469A4/en not_active Withdrawn
- 2003-11-28 AU AU2003303281A patent/AU2003303281A1/en not_active Abandoned
- 2003-11-28 CN CNA2003801044223A patent/CN1717598A/zh active Pending
- 2003-11-28 TW TW092133483A patent/TW200500335A/zh unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0540027A2 (en) * | 1991-10-31 | 1993-05-05 | Daicel Chemical Industries, Ltd. | Compositions, expoxidized compositions, a heat-curable resin composition, an epoxy resin composition, radically polymerized composition, a curable resin composition and a polymer having epoxy groups |
JPH09179296A (ja) * | 1995-12-22 | 1997-07-11 | Mitsubishi Chem Corp | 光重合性組成物 |
Non-Patent Citations (1)
Title |
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See also references of EP1571469A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101154039B (zh) * | 2006-09-25 | 2012-05-23 | 富士胶片株式会社 | 可固化组合物、滤色器及其制造方法 |
JP2008165059A (ja) * | 2006-12-28 | 2008-07-17 | Fujifilm Corp | 硬化性組成物、カラーフィルタ及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
TW200500335A (en) | 2005-01-01 |
EP1571469A4 (en) | 2006-12-20 |
AU2003303281A1 (en) | 2004-07-14 |
KR20050086893A (ko) | 2005-08-30 |
US20060257759A1 (en) | 2006-11-16 |
CN1717598A (zh) | 2006-01-04 |
EP1571469A1 (en) | 2005-09-07 |
JPWO2004057380A1 (ja) | 2006-04-27 |
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