Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/201—Filters in the form of arrays
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
  • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
• • G—PHYSICS
  • 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
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • 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
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/30—Devices specially adapted for multicolour light emission
  • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]

Definitions

• the present invention relates to a colored resin composition for forming pixels such as blue, red, and green, a color filter formed using the same, a liquid crystal display device formed using the color filter, and an image sensor (CCD, CMOS). ), And an electronic display device such as an organic EL display.
• liquid crystal display elements such as liquid crystal displays (LCD) typified by notebook computers, liquid crystal televisions, mobile phones, etc., and image sensors (CCD, CMOS) used as input devices for digital cameras, color copiers, etc.
• a color filter is required.
• As a method for producing a color filter used in these liquid crystal display devices and solid-state image sensors there are a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, and the like. In recent years, the pigment dispersion method has become the mainstream.
• a patterning method a photolithography method is typical, and a color filter is formed using a mixture of a photosensitive resin composition and a pigment dispersion.
• a method of forming a color filter by applying a colored ink directly on a substrate without using a mask by an ink jet printer is also performed.
• Improvement of color purity, saturation, brightness, and contrast, which are characteristics required for color filters, is particularly important.
• the amount of light of the backlight can be suppressed and the power consumption can be reduced, so this is an environmentally necessary technology.
• In order to improve the color purity of the color filter it is necessary to increase the content of the color pigment or to select a pigment having a better spectral waveform.
• the pigment concentration must be reduced or the film thickness must be reduced. In order to achieve both of these contradictory characteristics, a method of making pigment fine particles has been performed. As micronization progresses, there is a limit to the resistance and dispersion stability, and even when the brightness is improved, the compatibility of resistance is not achieved.
• JP-A-8-94826 Japanese Patent Laid-Open No. 2002-14222 JP 2010-32999 A Japanese Patent Laid-Open No. Sho 63-172772
• An object of the present invention is to provide a color filter which is excellent in color characteristics such as lightness and has excellent heat resistance and light resistance.
• the present inventor has found that the above problems can be solved by using a colored resin composition containing a specific color material compound in order to produce a pixel of a color filter.
• the present invention has been completed.
• the present invention A colored resin composition for a color filter containing a colorant compound represented by the following formula (1), a binder resin, a solvent, and a curing agent,
• R 1 to R 6 each independently represents a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a nitro group, a carboxyl group, or an alkoxycarbonyl group.
• Y 1 to Y 4 each independently represents a hydrogen atom, a C1-C12 alkyl group or an aryl group
• X 1 to X 5 each independently represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen atom It represents an alkylsulfonyl methide anion having a higher halogenated alkyl C1-C10 -.
• the colored resin composition of the present invention can provide a high-quality color filter excellent in lightness and heat resistance by using a specific colorant compound in the colored resin composition.
• the colored resin composition of the present invention contains a binder resin, a solvent, a curing agent, a specific color material compound, and if necessary, a color material such as other pigment or dye, a surfactant, a photopolymerization initiator, Various additives such as a thermal polymerization initiator, a polymerization inhibitor, and an ultraviolet absorber can be contained, but the present invention is not limited to these, and components other than the specific color material compound can be used without any particular limitation.
• the pixel manufacturing method using the colored resin composition of the present invention mainly includes a photolithography method and an inkjet method, and the former uses a photosensitive resin composition having excellent developability using a photopolymerization initiator.
• the latter does not necessarily require a photopolymerization initiator, and a thermosetting resin composition is used.
• R 1 to R 6 of the colorant compound represented by the formula (1) that can be used in the present invention are each independently a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, or a nitro group. Represents a carboxyl group or an alkoxycarbonyl group.
• Y 1 to Y 4 each independently represent a hydrogen atom, a C1-C12 alkyl group, or an aryl group.
• X 1 to X 5 are each independently a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen atom, a nitro group, a phenoxy group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfo group, or a sulfamoyl group.
• Anion Z - is representative of the methide anion with a higher halogenated alkyl C1-C10.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• alkyl group examples include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, iso-butyl, n-pentyl, n-hexyl, n-octyl, 2 -C1-C12 alkyl groups such as ethylhexyl and cyclohexyl. These alkyl groups may have a substituent.
• alkyl group having the substituent examples include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a 2-sulfoethyl group, a carboxyethyl group, a cyanoethyl group, a methoxy group. Examples thereof include an ethyl group, an ethoxyethyl group, a butoxyethyl group, a trifluoromethyl group, and a pentafluoroethyl group.
• the substituent that the alkyl group may have includes a carbamoyl group, a carboxyl group, and the like.
• alkoxy group examples include alkoxy groups having the same C1-C12 alkyl group as the alkyl group, and alkoxycarbonyl groups also include alkoxycarbonyl groups having the C1-C12 alkyl group.
• aryl group examples include aromatic hydrocarbon residues such as phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, and benzopyrenyl; pyridyl, pyrazyl, pyrimidyl, quinolyl, isoquinolyl, pyrrolyl Groups, indoleenyl groups, imidazolyl groups, carbazolyl groups, thienyl groups, furyl groups and other aromatic heterocyclic residues.
• aryl groups may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a sulfo group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, and a cyano group.
• the above phenoxy group may have a substituent, and examples of the substituent include a C1-C12 linear or branched alkyl group, a halogen atom, an amino group, an alkylamino group, and a hydroxyl group.
• alkoxycarbonyl group examples include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, isobutyloxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, and cyclopentyloxycarbonyl.
• the carbamoyl group may have a substituent, and examples of the substituent include a C1-C12 substituted or unsubstituted linear or branched alkyl group, a phenyl group, a benzyl group, a tosyl group, and a pyrimidinyl group. It is done. Further, the carbamoyl group includes an aliphatic group in which two alkyl groups bonded to nitrogen have a C3-C12 cycloalkyl ring in combination with the nitrogen atom, or one or more heteroatoms such as nitrogen, oxygen, and sulfur. A family heterocycle can be formed.
• sulfo group examples include methanesulfonyl, ethanesulfonyl, hexanesulfonyl, decanesulfonyl and the like.
• sulfamoyl group examples include sulfamoyl, methanesulfamoyl, ethanesulfamoyl, propanesulfamoyl, isopropanesulfamoyl, butanesulfamoyl, isobutanesulfamoyl, pentansulfamoyl, isopentanesulfamoyl, Neopentanesulfamoyl, cyclopentanesulfamoyl, hexanesulfamoyl, cyclohexanesulfamoyl, heptanesulfamoyl, cycloheptanesulfamoyl, octanessulfamoyl, 2-ethylhexanesulfamoyl, 1,5- Dimethylhexanesulfamoyl, cyclooctanesulfamoyl, nonanesulfamoyl,
• Z in the general formula (1) - is representative of the methide anion with a higher halogenated alkyl group C1-C10, especially tris trifluoromethanesulfonyl methide anion are preferred.
• the colorant compound used in the colored resin composition of the present invention can be obtained, for example, by a known synthesis method described in Yutaka Hosoda “Theoretical Manufacturing Dye Chemistry” (pages 373 to 375) issued by Gihodo Co., Ltd. It is also possible to synthesize by purchasing a commercial product in which Z ⁇ is a chlorine anion and adding a corresponding salt or acid to perform salt exchange.
• the colorant compound in the present invention is synthesized by salt exchange
• a reaction solvent for example, water, methanol, ethanol, isopropanol, acetone, N, N-dimethylformaldehyde.
• water-soluble polar solvents such as amide (hereinafter abbreviated as DMF) and N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), and these solvents may be used alone or in combination.
• the salt or acid to be added is added in an amount of about 0.5 to 3 equivalents, stirred at a predetermined temperature (for example, 0 to 100 ° C.), can be easily synthesized, and the precipitated crystals are obtained by filtration.
• the coloring material compound represented by the formula (1) indicates the total solid content (the total amount of the solid content composed of the coloring material compound, the binder resin, the curing agent, etc.). .) Is preferably 1 to 60 parts by mass, more preferably 5 to 30 parts by mass. When the content is larger than this range, problems such as precipitation and aggregation occur, or the adhesiveness with the substrate is lowered due to insufficient curing. When the content is small, there is no big problem, but there is a possibility that sufficient color purity cannot be obtained as color characteristics.
• the colorant compound represented by the formula (1) When the colorant compound represented by the formula (1) has low solubility in the colored resin composition, it may be used after being dispersed with a dispersant, as in the case of the optional component pigment described later. Good. Two or more colorant compounds represented by the formula (1) may be mixed or used alone, but other dyes or pigments may be mixed. Since the present invention mainly relates to blue pixels and red pixels, if necessary, it can be mixed with known blue dyes, violet dyes, red dyes and yellow dyes, or blue pigments, violet pigments, red pigments and yellow pigments. .
• the binder resin used in the present invention is desirably soluble in an alkaline developer used in a development processing step during the production of a color filter in terms of the design of a photolithography method, and further, to form a good fine pattern. Those having sufficient curing characteristics with a photopolymerization initiator, a photopolymerizable monomer and the like are desirable.
• the pigment-dispersed resin composition must also have good compatibility with constituent materials such as a photopolymerization initiator, a photopolymerizable monomer, and a pigment dispersion, and be stable so as not to cause precipitation or aggregation. In the case of the inkjet method, alkali solubility is not particularly required, and therefore a resin having good compatibility with other colorants and additives may be selected.
• a known resin can be used as the binder resin, but more preferably one or more of the following carboxyl groups or ethylenically unsaturated monomers having a hydroxyl group or other copolymerizable aromatic hydrocarbon groups. And a copolymer such as an ethylenically unsaturated monomer having an aliphatic hydrocarbon group.
• those having an epoxy group at the side chain or terminal, and epoxy acrylate resins to which acrylate is added can also be used. These monomers may be used alone or in combination of two or more.
• hydroxyl group-containing ethylenically unsaturated monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 4-hydroxypentyl (meth) acrylate, 3-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate , 5-hydroxyhexyl (meth) acrylate, 4-hydroxyhexyl (meth) acrylate, 5-hydroxy-3-methyl-pentyl (meth) acrylate, cyclohexane-1,4-dimethanol-mono (meth) acrylate Hydroxyl groups such as relate, 2- (2-hydroxyethyloxy) ethyl (meth) acrylate,
• Examples of the other copolymerizable ethylenically unsaturated monomers include styrene, ⁇ -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, and m-chloro.
• Aromatic vinyl compounds such as styrene, p-chlorostyrene, p-methoxystyrene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl ( (Meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, paracumylphenoxyethylene glycol (meta ) Acrylate, 2-hydroxy -3-unsaturated carboxylic acid esters such as phenoxypropyl (meth) acrylate, o-phenylphenol glycidyl ether (meth) acrylate, o-phenylphenol (meth) acrylate
• Carboxylic acid vinyl esters unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, vinylidene cyanide Acrylamide, methacrylamide, ⁇ -chloroacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, N- (meth) acryloylphthalimide, N- (2-hydroxyethyl) a Unsaturated amides or unsaturated imides such as rilamide, N- (2-hydroxyethyl) methacrylamide and maleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl acrylate and polymethyl Examples thereof include macromonomers having a
• a polymer in which an unsaturated double bond is further introduced into the side chain of the copolymer is also useful.
• an acrylate having an alcoholic hydroxyl group such as hydroxyethyl acrylate in the maleic anhydride portion of a copolymer with styrene, vinylphenol, acrylic acid, acrylic ester, acrylamide, or the like copolymerizable with maleic anhydride
• Acrylic acid is added to the hydroxyl group of a compound obtained by reacting an acrylate having an epoxy group, such as glycidyl methacrylate, and half-esterified, and a copolymer of acrylic acid, an acrylic ester and an acrylate having an alcoholic hydroxyl group such as hydroxyethyl acrylate.
• urethane resin, polyamide, polyimide resin, polyester resin commercially available ACA-200M (manufactured by Daicel), ORGA-3060 (manufactured by Osaka Organic Chemical), AX3-BNX02 (manufactured by Nippon Shokubai), UXE-3024 (Nippon Kayaku) UXE-3000 (Nippon Kayaku), ZGA-287H (Nippon Kayaku), TCR-1338H (Nippon Kayaku), ZXR-1722H (Nippon Kayaku), ZFR-1401H (Nippon Kayaku) And ZCR-1642 (manufactured by Nippon Kayaku) can also be used.
• a dispersant and a dispersion aid are used when dispersing a pigment.
• pigment-based dispersants resin-based dispersants, surfactants, and the like having good adsorptivity to pigments.
• a pigment-based dispersant a method of mixing a sulfonated pigment or a metal salt thereof as described in Patent Document 4 with a pigment, a method of mixing a substituted aminomethyl derivative, and the like are known as known techniques.
• Some resin dispersants are nonpolar nonionic, but polymer resins having an acid value, an amine value, etc. that give good pigment adsorption are common, such as acrylic resins, polyurethane resins, and polycarboxylic acids.
• Polyamide resin Polyamide resin, polyester resin and the like.
• Specific examples thereof include ED211 (manufactured by Enomoto Kasei), Ajisper PB821 (manufactured by Ajinomoto Fine Techno), Solsperse 71000 (manufactured by Avicia), and the like.
• a polymerization initiator When producing the binder resin (copolymer) used in the present invention, a polymerization initiator is used.
• the polymerization initiator used when synthesizing the copolymer include ⁇ , ⁇ ′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), Examples thereof include t-butyl peroctoate and di-t-butyl peroxide benzoylmethyl ethyl ketone peroxide.
• the use ratio of the polymerization initiator is 0.01 to 25 parts by mass with respect to the total of all monomers used for the synthesis of the copolymer.
• the reaction temperature when synthesizing the copolymer is preferably 50 to 120 ° C., particularly preferably 80 to 100 ° C.
• the reaction time is preferably 1 to 60 hours, more preferably 3 to 20 hours.
• the preferred acid value of the copolymer is 10 to 300 (mgKOH / g), and the preferred hydroxyl value is 10 to 200 (mgKOH / g). When the acid value or hydroxyl value is 10 or less, developability is lowered.
• the weight average molecular weight (Mw) of the copolymer is preferably from 2,000 to 400,000, more preferably from 3,000 to 100,000. When the weight average molecular weight is 2000 or less, or 400000 or more, sensitivity, developability and the like are lowered.
• the binder resins can be used alone or in admixture of two or more.
• the content of the binder resin in the present invention is usually 0.5 to 99 parts by mass, preferably 5 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the colored resin composition. In this case, if the content of the binder resin is less than 0.5 parts by mass, the alkali developability may be lowered, or problems such as scumming or film residue in areas other than the area where pixels are formed may occur. is there.
• the curing agent used in the present invention includes a photopolymerization monomer in the case of radical polymerization, an epoxy resin in the case of ion curing, and a melamine curing agent.
• a photopolymerization monomer in the case of radical polymerization
• an epoxy resin in the case of ion curing
• a melamine curing agent include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol (Meth) acrylate, tetraethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol
• the dye that can be used in addition to the essential components in the colored resin composition of the present invention preferably has spectral characteristics suitable for a color filter, and can be appropriately selected from dyes, organic pigments, and inorganic pigments. It can also be used alone or in combination of two or more. These contents are 0 to 60 parts by mass, preferably 5 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the colored resin composition. These various pigments and dyes are shown below.
• the organic pigment that can be used in addition to the essential components in the colored resin composition of the present invention is not particularly limited.
• pigments such as pigments; lake pigments in which acid dyes, basic dyes, direct dyes and the like are insolubilized with respective precipitants, dyed lake pigments, and the like.
• the color index for example, Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76 78, 79, Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29 31, 32, 37, 39, 42, 44, 47, 49, 50, Pigment Violet 3, 4, 27, 39, Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48 : 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 8 : 5, 122, 146, 168, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 279, Pigment
• the inorganic pigment that can be used in combination with the essential components in the colored resin composition of the present invention is not particularly limited, but examples thereof include composite metal oxide pigments, carbon black, black low-order titanium oxide, titanium oxide, barium sulfate, and zinc white.
• Examples thereof include oxides, metal sulfides, sulfates, metal hydroxides, and metal carbonates.
• the dye that can be used in addition to the essential components in the colored resin composition of the present invention is not particularly limited, and examples thereof include acid dyes, basic dyes, direct dyes, sulfur dyes, vat dyes, naphthol dyes, reactive dyes, and disperse dyes. It is done. Among them, any dye that is soluble in an organic solvent may be used, but even a dye that is insoluble in an organic solvent can be appropriately used by forming a dispersion. Dyes that are insoluble in organic solvents are well-known formulations.
• organic amine compounds for example, n-propylamine, ethylhexylpropionate amine, etc.
• amine salt dyes or It is known that the organic amine compound is reacted with a sulfonic acid group to be modified into a dye having a sulfonamide group.
• amine-modified dyes can also be used in the colored resin composition of the present invention.
• Specific examples of the dye include a color index, for example, C.I. number basic blue 7, acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51.
• the photopolymerization initiator used in the colored resin composition of the present invention used in the photographic method is preferably one having sufficient sensitivity to ultraviolet rays emitted from an ultra-high pressure mercury lamp generally used as an exposure light source, and radical polymerization.
• a component of a polymerization accelerator called a sensitizer that can be cured with less exposure energy can be used in combination.
• the photopolymerization initiator that can be used is not particularly limited.
• benzyl benzoin ether
• benzoin butyl ether benzoin propyl ether
• benzophenone 3,3′-dimethyl-4-methoxybenzophenone
• benzoylbenzoic acid benzoylbenzoic acid.
• Acid esterified product 4-benzoyl-4'-methyldiphenyl sulfide, benzyldimethyl ketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, dimethylthioxanthone, diethylthioxanthone, diisopropyl Thioxanthone, dimethylaminomethylbenzoate, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, methylbenzoyl formate 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benz
• thermosetting resin composition used in an ink jet method or the like
• a thermal polymerization initiator is generally used, but it may be used in combination with a photopolymerization initiator if necessary.
• the thermal polymerization initiator include azo compounds and organic peroxides, such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), Examples include 2,2′-azobis (2-methylbutyronitrile), di-t-butyl peroxide, dibenzoyl peroxide, cumylperoxyneodecanoate, and the like.
• These initiators can be used alone or in combination of two or more as required. These contents are 0.5 to 50 parts by mass, preferably 1 to 25 parts by mass, when the solid content of the colored resinous composition is 100 parts by mass.
• the organic solvent used in the present invention has sufficient dissolving power with respect to the binder resin, photopolymerizable monomer, photopolymerization initiator, and the like, which are components of the colored resin composition, and is a monofunctional compound used for the synthesis of the binder resin. Those having sufficient dissolving power for monomers, polymerization initiators and the like can be used. Moreover, what can maintain dispersion stability can also be used when preparing a pigment dispersion.
• the organic solvent used in the present invention is not particularly limited as long as it can be used.
• Specific examples include benzenes such as benzene, toluene and xylene; cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; methyl cellosolve acetate.
• Cellosolve acetates such as ethyl cellosolve acetate and butyl cellosolve acetate; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate; methyl methoxypropionate, methoxypropion Propionates such as ethyl acrylate, methyl ethoxypropionate, ethyl ethoxypropionate; methyl lactate, milk Lactic acid esters such as ethyl and butyl lactate; Diethylene glycols such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; Acetic esters such as methyl acetate, ethyl acetate and butyl acetate; Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and
• the amount of the organic solvent used is preferably 40 to 10000 parts by mass, more preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the total solid content of the colored resin composition.
• the colored resin composition of the present invention is produced by mixing and stirring the binder resin, the curing agent, the specific color material compound, the organic solvent, and the like with a dissolver, a homomixer, or the like.
• a dispersion is obtained by a dispersing machine such as a paint shaker using an appropriate dispersant, In addition to the colored resin composition, it is mixed.
• the colored resin composition of the present invention may further include various additives, for example, fillers, surfactants, photopolymerization initiators, thermal polymerization initiators, polymerization inhibitors, adhesion promoters, antioxidants, as necessary.
• An ultraviolet absorber, an aggregation inhibitor, etc. can be added.
• the colored resin composition of the present invention can be microfiltered with a filter or the like in order to remove foreign matters after the preparation.
• the colored resin composition of the present invention is formed on a glass substrate, a silicon substrate or the like by a method such as spin coating, roll coating, slit and spin, die coating, or bar coating. 1 to 20 ⁇ m, more preferably 0.5 to 5 ⁇ m, if necessary, in a vacuum chamber, drying conditions, temperature 23 to 150 ° C., time 1 to 60 minutes, more preferably temperature The film is dried under reduced pressure at 60 to 120 ° C. for 1 to 10 minutes, and further pre-baked with a hot plate or a clean oven to form a film.
• a method for preparing the cured product from the colored resin composition of the present invention will be described.
• the colored resin composition of the present invention is formed on a glass substrate, a silicon substrate or the like by a method such as spin coating, roll coating, slit and spin, die coating, or bar coating. 1 to 20 ⁇ m, more preferably 0.5 to 5 ⁇ m, if necessary, in a vacuum chamber, drying conditions, temperature 23 to 150 ° C
• radiation for example, an electron beam or ultraviolet rays, preferably ultraviolet rays
• a surfactant aqueous solution for example, an electron beam or ultraviolet rays, preferably ultraviolet rays
• a surfactant aqueous solution for example, an alkaline aqueous solution, or a mixture of a surfactant and an alkaline agent
• develop with aqueous solution Development methods include a dip method, a spray method, a shower method, a paddle method, and an ultrasonic development method, and any of these methods may be combined.
• the unirradiated portion is removed by development, rinsed with water, and then post-baked.
• the treatment is performed at a temperature of 130 to 300 ° C. for 1 to 120 minutes, more preferably at a temperature of 150 to 250 ° C. for 1 to 30 minutes. Under the condition, a pixel made of the colored cured film of the present invention is obtained.
• polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, etc. can be used as the surfactant.
• the alkali agent sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, or the like is used.
• an aqueous solution containing both an alkali agent and a surfactant is usually carried out at a processing temperature of 10 to 50 ° C., preferably 20 to 40 ° C., for a processing time of usually 30 to 600 seconds, preferably 30 to 120 seconds.
• the cured product of the colored resin composition of the present invention is useful as a color filter suitable for a liquid crystal display device, an organic EL display, a solid-state image sensor used in a digital camera, etc., and the color filter is as described above. It has the patterned pixel which consists of hardened
• the liquid crystal display device is produced with a structure in which, for example, a backlight, a polarizing film, a display electrode, a liquid crystal, an alignment film, a common electrode, a color filter of the present invention, a polarizing film, and the like are laminated in this order.
• An organic EL display is produced by forming the color filter of the present invention on either the upper or lower side of a multilayer organic light emitting device.
• the solid-state imaging device is manufactured by, for example, providing the color filter layer of the present invention on a silicon wafer provided with transfer electrodes and photodiodes, and then laminating microlenses.
• the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Further, the spectral transmittance was measured with a spectrophotometer “Shimadzu Corporation UV-3150”, the chromaticity in the XYZ color system was calculated, and the resistance of the colored body was evaluated.
• Synthesis example 1 In a 100 ml beaker, 1 g of rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.) of the following formula (100) and 20 g of water were charged and stirred at room temperature for 30 minutes. A solution prepared by dissolving 1 g of a cesium salt of tristrifluoromethanesulfonylmethide (TFSM) in 1 g of DMF was added dropwise thereto and stirred for 3 hours. The precipitated dye was collected by filtration, washed with water and dried, and compound No. 1 which is a TFSM salt of rhodamine B was used. 0.7 g of 1 was obtained. Maximum absorption wavelength: 560 nm (cyclohexanone)
• Synthesis example 2 A 100 ml beaker was charged with 1 g of rhodamine 6G (manufactured by Tokyo Chemical Industry Co., Ltd.) of the following formula (101) and 20 g of water and stirred at room temperature for 30 minutes. A solution prepared by dissolving 1 g of a cesium salt of tristrifluoromethanesulfonylmethide in 1 g of DMF was added dropwise thereto and stirred for 3 hours. The precipitated dye was collected by filtration, washed with water, and dried, and compound No. 1 which was a TFSM salt of rhodamine 6G. 0.8 g of 2 was obtained. Maximum absorption wavelength: 531 nm (cyclohexanone)
• Synthesis Example 3 (Preparation of binder resin (copolymer)) A 500 ml four-necked flask was charged with 160 g of methyl ethyl ketone, 10 g of methacrylic acid, 33 g of benzyl methacrylate, and 1 g of ⁇ , ⁇ ′-azobis (isobutyronitrile), and nitrogen gas was allowed to flow into the flask for 30 minutes while stirring. Thereafter, the temperature was raised to 80 ° C., and the mixture was stirred at 80 to 85 ° C. for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature to obtain a colorless, transparent and uniform copolymer solution.
• copolymer (A) This was precipitated in a 1: 1 mixed solution of isopropyl alcohol and water, filtered, and the solid content was taken out and dried to obtain a copolymer (A).
• the resulting copolymer (A) had a polystyrene equivalent weight average molecular weight of 18,000 and an acid value of 152.
• Example 1 5.4 g of copolymer (A) as a binder resin, 6 g of Kayrad DPHA (manufactured by Nippon Kayaku) as a photopolymerizable monomer, 1.5 g of Irgacure 907 (manufactured by BASF Japan) as a photopolymerization initiator, and Kayacure DETX-S ( Nippon Kayaku Co., Ltd.) 0.6 g, Compound No. of Synthesis Example 1 as a dye. 0.6 g of 1 and 20 g of cyclohexanone as a solvent and 8.6 g of propylene glycol monomethyl ether acetate were mixed to obtain a violet colored resin composition of the present invention.
• copolymer (A) as a binder resin
• 6 g of Kayrad DPHA manufactured by Nippon Kayaku
• Irgacure 907 manufactured by BASF Japan
• Kayacure DETX-S Nippon Kayaku Co., Ltd.
• Examples 2 to 3 were as follows.
• Example 2 Compound No. 1 of Synthesis Example 1 1 was synthesized as Compound No. 1 of Synthesis Example 2. Except for changing to 2, the same composition as in Example 1 was obtained to obtain a red colored resin composition.
• the pigment dispersion liquid 1 was obtained by processing for 60 minutes with a paint shaker and filtering. 19 g of pigment dispersion 1 was added to Example 1 to obtain a colored resin composition of the present invention.
• Comparative Example 1 Compound No. 1 of Synthesis Example 1 Except for changing 1 to rhodamine B, the same composition as in Example 1 was obtained to obtain a violet colored resin composition.
• Comparative Example 2 Compound No. 1 of Synthesis Example 1 A red colored resin composition was obtained with the same composition as in Example 1 except that 1 was changed to rhodamine 6G.
• Comparative Example 3 Compound No. 1 of Synthesis Example 1 A blue colored resin composition was obtained with the same composition as in Example 1 except that 1 was changed to Basic Blue 7.
• substrate for heat resistance evaluation apply
• the heat resistance was evaluated by measuring the transmittance of the substrate for evaluation using a spectrophotometer, treating the substrate for evaluation at 200 ° C. for 120 minutes, measuring the spectral transmittance again, and calculating the color difference ( ⁇ Eab). The results of heat resistance are shown in Table 2.
• Table 2 shows the evaluation results of heat resistance, but the heat resistance of Examples 1 to 3 of the present invention is significantly improved as compared with the conventional dyes of Comparative Examples 2 and 3.
• Example 3 the pigment was used in combination, but even when the colorant compound of the present invention having various color characteristics such as blue and red and the pigment were mixed, the result showed no particular precipitation. .
• the present invention can form a color filter with a colored resin composition using a specific colorant compound, and the obtained color filter has high resistance because it has sufficient resistance while being a dye. And clear pixels with high reliability can be obtained. In addition, it was found that it can be mixed well with pigments and other dyes depending on the application, and has high industrial value.

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