CN102472852A - Colored resin composition, colored cured film, color filter, display device and solid-state image sensor - Google Patents
Colored resin composition, colored cured film, color filter, display device and solid-state image sensor Download PDFInfo
- Publication number
- CN102472852A CN102472852A CN2011800030317A CN201180003031A CN102472852A CN 102472852 A CN102472852 A CN 102472852A CN 2011800030317 A CN2011800030317 A CN 2011800030317A CN 201180003031 A CN201180003031 A CN 201180003031A CN 102472852 A CN102472852 A CN 102472852A
- Authority
- CN
- China
- Prior art keywords
- methyl
- color filter
- resin composition
- colored resin
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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]
Abstract
Provided is a colored resin composition for creating highly-reliable color filter pixels having vivid and high-definition color characteristics, and having greater tolerance properties than the products of the prior art. The colored resin composition for creating highly-reliable color filter pixels can easily be obtained by using specific coloring compounds, and by mixing in binder resins, solvents, curing agents, and the like. The color filter pixels that are manufactured use dyes as coloring compounds, and are highly reliable and have excellent resistance properties such as thermal tolerance.
Description
Technical field
The present invention relates to form the pixel of blueness, redness and green etc. colored resin composition, use the color filter of its formation and use electronic display units such as liquid crystal indicator that this color filter forms, camera head (CCD, CMOS), organic el panel.
Background technology
Be the LCDs liquid crystal display cells such as (LCD) of representative, need color filter in the colorize of the camera head (CCD, CMOS) that uses as entering apparatus such as digital camera, color copy machines with notebook computer, liquid crystal TV set, mobile phone etc.Be used for the method for the color filter of these liquid crystal indicators, solid state image sensor as manufacturing, comprise decoration method, electro-deposition method, print process, pigment dispersing method etc., in recent years, the pigment dispersing method is just becoming main flow.As the method for patterning, photolithography is representational method, and the potpourri of its usability photosensitive resin composition and pigment dispersion forms color filter.Also carried out following method recently: do not utilize ink-jet printer directly coloring printing ink to be applied on the substrate, to form color filter across mask.
The desired characteristic of raising color filter---excitation, chroma, brightness and contrast are particular importances.Through improving brightness, can suppress the light quantity of backlight, can also reduce power consumption, be necessary technology therefore from the environment aspect.In order to improve the excitation of color filter, need to increase the content of coloring pigment, perhaps select the pigment of better spectrum (beam split waveform).On the other hand,, need to improve transmissivity, therefore must reduce pigment concentration on the contrary or reduce thickness in order to improve brightness.In order to take into account the characteristic that these are runed counter to, use the such method of micronize of pigment at present.Carry out along with micronized, there are the limit in patience and dispersion stabilization, and raising also can't obtain taking into account of patience even present situation is brightness.
In order to address these problems,, advancing the research of the color filter that uses dyestuff as another method.If use dyestuff, then have following advantage: can take into account pigment the excitation and the brightness that can't realize; Owing to be not particle, thereby can suppress light scattering, therefore can also improve contrast.But, when needing the display body of long-term reliability, need photostability and thermotolerance towards televisor etc. especially, but in dyestuff, particularly compare patience with pigment how obviously relatively poor for blue dyes.For example reported a kind of color filter that uses the triphenylmethane based compound in the patent documentation 1 and 2, but the photostability of triphenylmethane based compound, thermotolerance are obviously relatively poor, can't reach realistic scale.In addition, the brightness of having put down in writing the xanthene based compound in the patent documentation 3 is excellent, but does not have the record about the patience aspect.In needing the color filter of high reliability, need contain the colored resin composition of the excellent colorant compounds of patience, but present situation is equal practicability not almost.Therefore, people require brightness excellence and the excellent high-quality color filter of future generation of patience.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 8-94826 communique
Patent documentation 2: TOHKEMY 2002-14222 communique
Patent documentation 3: TOHKEMY 2010-32999 communique
Patent documentation 4: japanese kokai publication sho 63-172772 communique
Summary of the invention
The object of the present invention is to provide color excellent such as a kind of brightness and thermotolerance, color filter that photostability is excellent.
The inventor furthers investigate in order to solve above-mentioned problem, and the result finds, uses the colored resin composition that contains specific colorant compounds for the pixel of making color filter, can solve above-mentioned problem, has accomplished the present invention thus.
That is, the present invention relates to:
(1) a kind of color filter is used colored resin composition, and it contains colorant compounds, resin glue, solvent and the hardening agent of following formula (1) expression.
(in the formula (1), R
1～R
6Alkyl, the alkoxy of C1-C12, nitro, carboxyl, the alkoxy carbonyl of representing hydrogen atom, halogen atom, C1-C12 independently of one another.Y
1～Y
4Alkyl, the aryl of representing hydrogen atom, C1-C12 independently of one another.X
1～X
5Alkyl, the alkoxy of C1-C12, halogen atom, nitro, phenoxy group, carboxyl, alkoxy carbonyl, carbamyl, sulfo group, the sulfamoyl of representing hydrogen atom, C1-C12 independently of one another.Anionicsite Z
-Expression has the alkyl sulphonyl methide negative ion of the high halogenated alkyl of C1-C10.)
(2) use colored resin composition like (1) described color filter, wherein, the Z in the formula (1)
-It is three (trifluoromethane sulfonyl group) methide negative ion.
(3) like (1) or (2) described colored resin composition, it contains metal phthalocyanine pigment.
(4) a kind of color filter is used the color solidification film, and it carries out patterning through each the described colored resin composition that uses (1)～(3) and forms.
(5) a kind of color filter, it is processed with the color solidification film by (4) described color filter.
(6) a kind of display device, it is equipped with (5) described color filter and forms.
(7) a kind of solid state image sensor, it is equipped with (5) described color filter and forms.
Colored resin composition of the present invention can provide the high-quality color filter of a kind of brightness, excellent heat resistance through specific colorant compounds is used for colored resin composition.
Embodiment
Colored resin composition of the present invention contains resin glue, solvent, hardening agent, specific colorant compounds; Can contain various additives such as colorants such as other pigment or dyestuff, surfactant, Photoepolymerizationinitiater initiater, thermal polymerization, polymerization inhibitor, ultraviolet light absorber as required; But be not limited to this; As the composition except that specific colorant compounds, can not have especially restrictedly and use.
As the pixel manufacturing approach of using colored resin composition of the present invention; Mainly can enumerate photolithography and ink-jet method; The former has used the excellent photosensitive polymer combination of development property that utilizes Photoepolymerizationinitiater initiater, and the latter may not need Photoepolymerizationinitiater initiater and use hot curing resin composition.
The R of the colorant compounds of operable above-mentioned formula (1) expression among the present invention
1～R
6Alkyl, the alkoxy of C1-C12, nitro, carboxyl, the alkoxy carbonyl of representing hydrogen atom, halogen atom, C1-C12 independently of one another.Y
1～Y
4Alkyl, the aryl of representing hydrogen atom, C1-C12 independently of one another.X
1～X
5Alkyl, the alkoxy of C1-C12, halogen atom, nitro, phenoxy group, carboxyl, alkoxy carbonyl, carbamyl, sulfo group, the sulfamoyl of representing hydrogen atom, C1-C12 independently of one another.Anionicsite Z
-Expression has the sulfonyl methide negative ion of the high halogenated alkyl of C1-C10.
As above-mentioned halogen atom, for example, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom.
As abovementioned alkyl, for example, can enumerate the alkyl of C1-C12 such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, isobutyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, cyclohexyl etc.These alkyl can have substituting group; As having this substituent alkyl; For example, can enumerate hydroxyethyl, hydroxypropyl, hydroxyl butyl, 2-sulfo group ethyl, carboxyethyl, cyano ethyl, methoxy ethyl, ethoxyethyl group, butoxyethyl group, trifluoromethyl, pentafluoroethyl group etc.In addition, this alkyl substituting group that can have comprises carbamyl, carboxyl etc.
As above-mentioned alkoxy, can enumerate the alkoxy of alkyl with C1-C12 identical with abovementioned alkyl, alkoxy carbonyl also can be enumerated the alkoxy carbonyl of the alkyl with identical C1-C12.
As above-mentioned aryl, can enumerate for example aromatic hydrocarbon residues such as phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, benzo pyrenyl; Heteroaromatic residues such as pyridine radicals, pyrazinyl, pyrimidine radicals, quinolyl, isoquinolyl, pyrrole radicals, indyl, imidazole radicals, carbazyl, thienyl, furyl etc.These aryl can have substituting group, as this substituting group, for example, can enumerate alkyl, alkoxy, halogen atom, sulfo group, carboxyl, alkoxy carbonyl, carbamyl, cyanic acid etc.
Above-mentioned phenoxy group can have substituting group, as substituting group, for example, can enumerate straight or branched alkyl, halogen atom, amino, alkyl amino, hydroxyl of C1-C12 etc.
As above-mentioned alkoxy carbonyl, for example can enumerate methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, isopropoxy carbonyl, butoxy carbonyl, isobutoxy carbonyl, pentyloxy carbonyl, isoamoxy carbonyl, neopentyl oxygen carbonyl, cyclopentyloxy carbonyl, hexyloxy carbonyl, cyclohexyloxy carbonyl, heptan oxygen base carbonyl, ring oxygen base carbonyl in heptan, carbonyl octyloxy, 2-ethyl hexyl oxy carbonyl, ring carbonyl octyloxy, ninth of the ten Heavenly Stems oxygen base carbonyl, last of the ten Heavenly stems oxygen base carbonyl, three ring oxygen base carbonyls in the last of the ten Heavenly stems, methoxy propoxy carbonyl, ethoxy propoxycarbonyl, own oxygen base propoxycarbonyl, 2-ethyl hexyl oxy propoxycarbonyl, methoxyl hexyloxy carbonyl, benzyloxycarbonyl, etc.
Above-mentioned carbamyl can have substituting group, as substituting group, can enumerate the replacement of C1-C12 or not have substituted straight or branched alkyl, phenyl, benzyl, tosyl, pyrimidine radicals etc.In addition, as above-mentioned carbamyl, with 2 alkyl of nitrogen bonding can with this nitrogen-atoms form C3-C12 cycloalkyl ring, or have the heteroatomic aliphatics heterocycle more than a kind in nitrogen, oxygen, the sulphur etc.
As above-mentioned sulfo group, can enumerate for example methane sulfonyl, ethane sulfonyl, hexane sulfonyl, decane sulfonyl etc.
As above-mentioned sulfamoyl; Can enumerate for example sulfamoyl, methane sulfamoyl, ethane sulfamoyl, propane sulfamoyl, different propane sulfamoyl, butane sulfamoyl, isobutane sulfamoyl, pentane sulfamoyl, isopentane sulfamoyl, neopentane sulfamoyl, cyclopentane sulfamoyl, hexane sulfamoyl, cyclohexane sulfamoyl, heptane sulfamoyl, cycloheptane sulfamoyl, octane sulfamoyl, 2-ethyl hexane sulfamoyl, 1,5-dimethylhexane sulfamoyl, cyclooctane sulfamoyl, nonane sulfamoyl, decane sulfamoyl, tristane sulfamoyl, methoxy propane sulfamoyl, ethoxy propane sulfamoyl, propoxyl group propane sulfamoyl, isopropoxy propane sulfamoyl, own oxygen base propane sulfamoyl, 2-ethyl hexyl oxy propane sulfamoyl, methoxyhexane sulfamoyl, 3-phenyl-1-methylpropane sulfamoyl etc.
In the general formula (1), Z
-Expression has the sulfonyl methide negative ion of the high halogenated alkyl of C1-C10, preferred especially three (trifluoromethane sulfonyl group) methide negative ion.
The colored resin composition of the invention is the use of compounds such as toner by Gihodo Co., fine Feng issued the "Theory manufacture of dyes Chemistry" (373 - 375) described in the synthesis method to obtain a known, but may acquire the anion Z-is commercially available chlorine and add the corresponding salt or acid salt exchange with synthesis.
During through the colorant compounds among the synthetic the present invention of salt exchange, for example, with Z
-For the colorant compounds of cl anion (for example is dissolved in reaction dissolvent; Can enumerate water or methyl alcohol, ethanol, isopropyl alcohol, acetone, N; Dinethylformamide (being designated hereinafter simply as DMF), N-N-methyl-2-2-pyrrolidone N-water soluble polar solvent such as (being designated hereinafter simply as NMP), these solvents can use separately or mix.) in, the salt or the acid of the correspondence about adding 0.5～3 equivalent are stirred down at predetermined temperature (for example 0～100 ℃), can synthesize easily, and filter the crystallization of separating out, thereby obtain.
The object lesson of above-mentioned formula (1) expression is shown in following table 1-1 and shows among the 1-2, but the present invention is not limited thereto.
[table 1]
Table 1-1
Table 1-2
Colored resin composition of the present invention is in the total solid composition (total amount of the solid constituent that refers to be made up of colorant compounds, resin glue, hardening agent etc.Hereinafter also use with identical meanings.) in contain and be preferably 1～60 mass parts, the composition of the colorant compounds of above-mentioned formula (1) expression of 5～30 mass parts more preferably.Content is during more than this scope, can separate out, problem such as cohesion, perhaps insufficiently causes that the adaptation with substrate reduces because of solidifying.Though content does not have bigger problem after a little while,, possibly can't obtain sufficient excitation as chromatic characteristic.
When the dissolubility of colorant compounds in colored resin composition of above-mentioned formula (1) expression is low, can with after state any composition---pigment likewise uses spreading agent to disperse the back to use it.The colorant compounds of above-mentioned formula (1) expression can mix use more than 2 kinds, also can use separately, can also mix other dyestuffs, pigment.The present invention relates generally to blue pixel, red pixel, also can mix with known blue dyes, cudbear, orchil, weld or blue pigment, violet pigment, red pigment, yellow uitramarine etc. as required.
The resin glue that uses among the present invention is expected in the design of photolithography in the alkaline soluble property developer solution; Development treatment operation when this alkaline-based developer is used for the color filter manufacturing; In order to form good fine pattern, expectation has the characteristic of fully solidifying with Photoepolymerizationinitiater initiater, photopolymerization monomer etc. in addition.In addition, the pigment dispersing resin composition is also good with the compatibility of constituent materials such as Photoepolymerizationinitiater initiater, photopolymerization monomer, dispersible pigment dispersion, separates out in order not cause, cohesion etc., must be stable.Under the situation of ink-jet method, do not need alkali solubility especially, select to get final product with the good resin of compatibility of other colorants, adjuvant.
As resin glue; Also can use known resin, but the multipolymer of the ethylenically unsaturated monomers with aromatic hydrocarbyl or aliphatic alkyl of the ethylenically unsaturated monomers of enumerating more preferably or other copolymerization etc. with 1 above carboxyl or hydroxyl.Side chain or end that in addition, can also use them etc. have epoxy radicals resin and then addition the Epocryl of acrylic ester.These monomers etc. can use separately, also can be with making up more than 2 kinds.
As the operable above-mentioned object lesson that contains the ethylenically unsaturated monomers of carboxyl among the present invention, can enumerate unsaturated monocarboxylic classes such as acrylic acid, methacrylic acid, butenoic acid, α-Lv Bingxisuan, 2-ethylacrylic acid, cinnamic acid; Unsaturated dicarboxylics (acid anhydrides) such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid class; Unsaturated polybasic carboxylic acid (acid anhydrides) class more than 3 yuan, 2-(methyl) acryloxy ethyl hexahydro-phthalic acid, 2-methacryloxyethyl 2-hydroxypropyl phthalic ester, 2-acryloxy ethyl 2-hydroxyethyl phthalic acid etc., they can separately or mix 2 kinds with on use.
As the operable above-mentioned object lesson that contains the ethylenically unsaturated monomers of hydroxyl among the present invention; Can enumerate (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 3-hydroxypropyl acrylate, (methyl) acrylic acid 4-hydroxy butyl ester, (methyl) acrylic acid 3-hydroxy butyl ester, (methyl) acrylic acid 5-hydroxy pentane ester, (methyl) acrylic acid 4-hydroxy pentane ester, (methyl) acrylic acid 3-hydroxy pentane ester, the own ester of (methyl) acrylic acid 6-hydroxyl, the own ester of (methyl) acrylic acid 5-hydroxyl, the own ester of (methyl) acrylic acid 4-hydroxyl, (methyl) acrylic acid 5-hydroxy-3-methyl-pentyl ester, cyclohexane-1; 4-dimethanol-list (methyl) acrylic ester, (methyl) acrylic acid 2-(2-hydroxyethyl oxygen base) ethyl ester, glycerin monomethyl acrylic ester, polyethyleneglycol (methyl) acrylic ester, polypropylene glycol list (methyl) acrylic ester, gather C-terminal ployalkylene glycol list (methyl) acrylic ester such as (ethylene glycol and 1,2-propylene glycol) monomethacrylates etc., they can separately or mix 2 kinds with on use.
In addition; But ethylenically unsaturated monomers as above-mentioned other copolymerization; For example, can enumerate styrene, AMS, adjacent vinyltoluene, a vinyltoluene, to vinyltoluene, chloro styrene, m-chlorostyrene, to chlorostyrene, to aromatic ethenyl compounds such as methoxy styrenes; (methyl) methyl acrylate; (methyl) ethyl acrylate; (methyl) acrylic acid n-propyl; (methyl) isopropyl acrylate; (methyl) n-butyl acrylate; (methyl) isobutyl acrylate; (methyl) sec-butyl acrylate; (methyl) tert-butyl acrylate; (methyl) acrylic acid 2-hydroxyl ethyl ester; (methyl) benzyl acrylate; To cumyl phenoxy group monoethylene glycol (methyl) acrylic ester; (methyl) acrylic acid 2-hydroxyl-3-phenoxy group propyl ester; O-phenyl phenol glycidol ether (methyl) acrylic ester; O-phenyl phenol (methyl) acrylic ester hydroxyethyl thing; Unsaturated carboxylate types such as (methyl) acrylic acid phenoxy ethyl; (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 3-methyl cyclohexanol ester, (methyl) acrylic acid norborneol ester, (methyl) acrylic acid norborny methyl esters, (methyl) acrylic acid phenyl norborneol ester, (methyl) acrylic acid cyanic acid norborneol ester, (methyl) IBOA, (methyl) acrylic acid norbornene ester, (methyl) acrylic acid menthyl ester, (methyl) acrylic acid fenchol ester, (methyl) acrylic acid diamantane ester, (methyl) acrylic acid dimethyladamantane ester, (methyl) acrylic acid three ring [5.2.1.02; 6] last of the ten Heavenly stems-8-base ester, (methyl) acrylic acid three rings [5.2.1.02,6] last of the ten Heavenly stems-alicyclic ring skeleton classes such as 4-methyl ester, (methyl) acrylic acid ring ester in the last of the ten Heavenly stems, 2-(methyl) acryloxy ethyl hexahydro-phthalic acid, (methyl) acrylic acid tert-butyl group cyclohexyl; Polyethyleneglycol (methyl) acrylic ester, polypropylene glycol list (methyl) acrylic ester, gather C-terminal ployalkylene glycol list (methyl) esters of acrylic acids such as (ethylene glycol and 1,2-propylene glycol) monomethacrylates; Terminal ployalkylene glycol list (methyl) esters of acrylic acid of alkyl such as methoxy poly (ethylene glycol) monomethacrylates, bay oxygen base polyethyleneglycol (methyl) acrylic ester, octyloxy polyglycol polypropylene glycol list (methyl) acrylic ester, Nonylphenoxy polyglycol mono acrylic ester, Nonylphenoxy polypropylene glycol mono acrylic ester, allyloxy polyethylene glycol-propylene glycol list (methyl) acrylic ester; Unsaturated carboxylic acid aminoalkyl ester classes such as acrylic acid 2-amino ethyl ester, methacrylic acid 2-amino ethyl ester, the amino propyl ester of acrylic acid 2-, the amino propyl ester of methacrylic acid 2-, the amino propyl ester of acrylic acid 3-, the amino propyl ester of methacrylic acid 3-; Glycidyl acrylate, GMA, (methyl) acrylic acid 3; Unsaturated carboxylic acid ethylene oxidic ester classes such as 4-epoxy butyl ester, (methyl) acrylic acid (3, the 4-epoxycyclohexyl) methyl esters, (methyl) acrylic acid 4-hydroxy butyl ester glycidyl ether; Vinyl carboxylates classes such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate; Unsaturated ethers such as methoxy ethylene, ethyl vinyl ether, allyl glycidyl ether, methylallyl glycidyl ether; Vinyl cyanide based compounds such as vinyl cyanide, methacrylonitrile, α-Lv Bingxijing, vinylidene dinitrile; Unsaturated amides such as acrylic amide, Methacrylamide, α-chloropropene acid amides, N-phenylmaleimide, N-cyclohexyl maleimide, N-(methyl) acryloyl phthalimide, N-(2-hydroxyethyl) acrylic amide, N-(2-hydroxyethyl) Methacrylamide, maleimide or unsaturated acid imide; Aliphatics conjugated dienes such as 1,3-butadiene, isoprene, chlorbutadiene; The end of polymer molecular chains such as polystyrene, PMA, polymethylmethacrylate, the positive butyl ester of polyacrylic acid, Vinalac 5920, silicone has the big monomer class of single acryloyl group or monomethyl acryloyl group etc., they can separately or mix 2 kinds with on use.
In addition, further to introduce the polymkeric substance of unsaturated double-bond also be useful to the side chain of multipolymer.For example, but the maleic anhydride part that can enumerate the multipolymer between the styrene that makes maleic anhydride and copolymerization, vinylphenol, acrylic acid, acrylic ester, the acrylic amide etc. and the acrylic ester with alcohol hydroxyl group (such as hydroxy-ethyl acrylate etc.) or GMA etc. have acrylate reactions and the compound of half fatization of epoxy radicals; And make acrylic acid, acrylic ester and have hydroxyl and the compound that the acrylic acid reaction forms etc. of multipolymer of the acrylic ester (such as hydroxy-ethyl acrylate etc.) of alcohol hydroxyl group.In addition, can also use carbamate resins, polyamide, polyimide resin, vibrin, commercially available ACA-200M (manufacturing of Daicel society), ORGA-3060 (manufacturing of Osaka organic chemistry), AX3-BNX02 (Japanese catalyst manufacturing), UXE-3024 (Japanese chemical drug manufacturing), UXE-3000 (Japanese chemical drug manufacturing), ZGA-287H (Japanese chemical drug manufacturing), TCR-1338H (Japanese chemical drug manufacturing), ZXR-1722H (Japanese chemical drug manufacturing), ZFR-1401H (Japanese chemical drug manufacturing), ZCR-1642 (Japanese chemical drug manufacturing).
Usually use spreading agent, dispersing aid during dispersed color.Existence is spreading agent, resin system spreading agent, surfactant etc. to the pigment that pigment has good adsorption property.For example, be spreading agent with the sulfonated bodies of pigment such described in the above-mentioned patent documentation 4 or its slaine and pigment method of mixing, the method etc. of mixing the substituted-amino methyl-derivatives as pigment be known as known technology.As the resin system spreading agent; The material that also has non-polar nonionic to be; Be generally have the acid number that can give good pigment adsorption property, the macromolecule resin of amine value etc., can enumerate acrylic resin, urethane resin, polybasic carboxylic acid, polyamide, vibrin etc.As its object lesson, for example, can enumerate ED211 (nanmu originally changes into manufacturing), AJISPER PB821 (AJINOMOTO FINE TECHNO manufacturing), Solsperse71000 (ァ PVC シ ァ manufacturing) etc.
When making the resin glue (multipolymer) that uses among the present invention, use polymerization initiator.Object lesson as the polymerization initiator that uses when this synthetic copolymer; Can enumerate α; α '-azo two (isobutyronotrile), 2,2 '-azo two (2-methylbutyronitrile), peroxidating (2 ethyl hexanoic acid) tert-butyl ester, di-tert-butyl peroxide, benzoyl peroxide, methyl-ethyl-ketone peroxide etc.With respect to the total amount that is used for the synthetic whole monomers of multipolymer, the usage ratio of polymerization initiator is 0.01～25 mass parts.In addition, during synthetic copolymer, preferably use the organic solvent of following explanation: the organic solvent that used monofunctional monomer, polymerization initiator etc. is had sufficient dissolving power.Temperature of reaction during synthetic copolymer is preferably 50～120 ℃, is preferably 80～100 ℃ especially.In addition, the reaction time is preferably 1～60 hour, more preferably 3～20 hours.The preferred acid number of multipolymer is 10～300 (mgKOH/g), and preferred hydroxyl value is 10～200 (mgKOH/g).Acid number or hydroxyl value are 10 when following, the reduction of development property.The weight-average molecular weight of multipolymer (Mw) is preferably 2000～400000, and more preferably 3000～100000.This weight-average molecular weight is below 2000, or 400000 when above, reductions such as sensitivity and development property.
Among the present invention, above-mentioned resin glue can separately or mix use more than 2 kinds.The content of the resin glue among the present invention is generally 0.5～99 mass parts with respect to the total solid composition of 100 mass parts colored resin compositions, is preferably 5～50 mass parts.In this case, if the content of resin glue is lower than 0.5 mass parts, then alkali development reduces, and perhaps may occur in to occur problems such as scum silica frost or film be residual in the zone beyond the part that forms pixel.
As the hardening agent that uses among the present invention, can enumerate photo polymerization monomer under the situation of free radical polymerization, can enumerate epoxy resin under the situation that ion solidifies, also have melamine cured dose etc. in addition.Their object lesson can be enumerated (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) 2-EHA, ethylene glycol bisthioglycolate (methyl) acrylic ester, diglycol two (methyl) acrylic ester, triethylene glycol (methyl) acrylic ester, tetraethylene glycol (methyl) acrylic ester, trimethylolpropane tris (methyl) acrylic ester, pentaerythrite two (methyl) acrylic ester, pentaerythrite three (methyl) acrylic ester, pentaerythrite four (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester, glycerine (methyl) acrylic ester, bisphenol-A type epoxy two (methyl) acrylic ester, bisphenol-f type epoxy two (methyl) acrylic ester, bis-phenol-fluorenes type epoxy two (methyl) acrylic ester, ethoxylated trimethylolpropane three (methyl) acrylic ester, propoxylation trimethylolpropane tris (methyl) acrylic ester, ethoxylated glycerol three (methyl) acrylic ester, ethoxylation isocyanuric acid three (methyl) acrylic ester, double trimethylolpropane four (methyl) acrylic ester, ethoxylation pentaerythrite four (methyl) acrylic ester, 9, two [4-(the 2-acryloyl-oxy base oxethyl) phenyl] fluorenes of 9-, KAYARAD RP-1040 (Japanese chemical drug manufacturing), KAYARAD DPCA-30 (Japanese chemical drug manufacturing), UA-33H (Xin Zhong village chemistry is made), UA-53H (Xin Zhong village chemistry is made), M-8060 (East Asia is synthetic makes); As mercaptan is TEMPIC (the Sakai chemistry is made), TMMP (the Sakai chemistry is made), PEMP (the Sakai chemistry is made), the DPMP (the Sakai chemistry is made) of polymerization single polymerization monomer; As the Japanese chemical drug goods NC-6000 of epoxy resin, NC-3000, EOCN-1020, XD-1000, EPPN-501H, BREN-S, NC-7300L, Daicel chemical goods CELLOXIDE 2021P, EHPE3150, Cyclomer M100, EPOLEAD PB3600, japan epoxy resin goods Epikote 828, Epikote YX8000, Epikote YX4000, Sila-Ace S510 (Chisso), TEPIC (daily output chemical industry) etc.; As melamine cured dose methylolation melamine, Mw-30 (Sanwa Chemical) etc.These hardening agent can separately or mix use more than 2 kinds.The content of these hardening agent is 1～80 mass parts with respect to the total solid composition of 100 mass parts colored resin compositions, is preferably 5～30 mass parts.
The pigment that can share the neccessary composition in colored resin composition of the present invention preferably has the dichroism that is suitable for color filter; Can from dyestuff, organic pigment, inorganic pigment, suitably select, also can use more than 2 kinds alone or in combination as required.With respect to the total solid composition of 100 mass parts colored resin compositions, the content of these pigments is 0～60 mass parts, is preferably 5～30 mass parts.These various pigment and dyestuffs below are shown.
As the organic pigment that can share the neccessary composition in colored resin composition of the present invention; Not special restriction; For example, can enumerate anthraquinone system, phthalocyanine system, triphenylmethane system, benzimidazolone system, quinacridone, azo chelating system, azo system, isoindoline system, isoindolinone system, pyranthrone system, indanthrone system, anthrapyrimidine system, dibromoanthracene is formed pigment such as anthrone system, flavanthrone system, perylene system, purple cyclic ketones system, quinophthalone system, thioindigo system, dioxazine system, quinacridone, xanthene system; Mordant pigment after usefulness such as acid dyes, basic-dyeable fibre, direct dyes precipitation agent separately do not dissolved, dyeing mordant pigment (dyeing lake pigment) etc.More particularly; In color index; For example, can enumerate 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, paratonere 7,14,41,48:1,48:2,48:3,48:4,57:1,81,81:1,81:2,81:3,81:4,81:5,122,146,168,177,178,184,185,187,200,202,208,210,246,254,255,264,270,272,279, pigment orange 43,71,73, pigment yellow 1,2,3,4,5,6,10,12,13,14,15,16,17,18,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,126,127,128,129,138,139,147,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,198,199,213,214, pigment Green 7,36,58, etc.Wherein, good pigment blue 15 such as preferred hue, patience, 15:1,15:2,15:3,15:4,15:6,16,17,75,76, metal phthalocyanine pigment such as 79; Pigment Violet 23, paratonere 177,254, pigment yellow 83,138,139,150, the pigment blue 15 of preferred especially CuPc pigment: 6.
As the inorganic pigment that can share the neccessary composition in colored resin composition of the present invention; Not special restriction; For example, can enumerate metal oxide, metal sulfide, sulfate, metal hydroxides, metal carbonates etc. such as composite metal oxide pigment, carbon black, black titanium suboxide, titania, barium sulphate, zinc white, lead sulfate, yellow lead, iron oxide red, ultramarine, Prussian blue, chromium oxide, stibium trioxide, iron oxide black, red lead, zinc sulphide, cadmium yellow, cadmium red, zinc, manganese violet, cobalt violet, barium sulphate, magnesium carbonate.
The not special restriction of the dyestuff that can share the neccessary composition in colored resin composition of the present invention can be enumerated acid dyes, basic-dyeable fibre, direct dyes, sulfur dye, vat dye, naphthol dye, reactive dye, disperse dyes etc.Wherein, get final product,, also can suitably use through processing dispersion even be insoluble to the dyestuff of organic solvent so long as dissolve in the dyestuff of organic solvent.As well-known prescription; The dyestuff that is insoluble to organic solvent is during for example for acid dyes; Knownly make organic amine compound (for example n-propylamine, ethylhexyl propionic acid amine etc.) reaction and modification becomes the amine salt dyestuff, its sulfonic group is reacted and modification becomes to have the dyestuff of sulfoamido etc. with same organic amine compound.The dyestuff of these amine modifications also can be used for colored resin composition of the present invention.As its concrete dyestuff; In color index, can enumerate the numbering of C.I. for example Blue 7, Blue VRS, 7,9,15,18,23,25,27,29,40,42,45,51,62,70,80,83,86,87,90,92,96,103,112,113,120,129,138,147,150,158,171,182,192,210,242,243,249,256,259,267,278,280,285,290,296,315,324,335,340, Blue 7,11,15,26, solvent blue 2,3,4,5,6,23,25,35,37,38,43,55,59,67,72,124, alkaline purple 10, acid violet 17,49, solvent violet 4,5,14, alkali red 1:1,10,29, acid red 91,92,97,114,138,151,289, solvent red 45,49,127, Indian yellow 17,23,25,29,38,40,42,76, solvent yellow 4,14,15,24,76,81,82,94,98,162, solvent orange 2,7,11,15,26,56, acid green 9,16, etc.
The Photoepolymerizationinitiater initiater that uses as the colored resin composition of the present invention that is used for photographic process; Preferably for having sufficient sensitivity person, can enumerate photoacid generator or the Photobase generator of free-radical polymerised optical free radical initiating agent, ion curable etc. by the ultraviolet ray of usually penetrating as the ultrahigh pressure mercury lamp of exposure light source.In the photopolymerization, can make up and make the composition of curing with still less exposure energy polymerization accelerant that be cured, that be called as sensitizer.The not special restriction of operable Photoepolymerizationinitiater initiater; As object lesson; Can enumerate dibenzoyl, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3; The carboxylate of 3 '-dimethyl-4-methoxy benzophenone, benzoylbenzoic acid, benzoylbenzoic acid, 4-benzoyl-4 '-methyldiphenyl thioether, benzoin dimethylether, 2-butoxyethyl group-4-methylamino benzoic ether, clopenthixal ketone, methyl thioxanthones, ethyl thioxanthones, isopropyl thioxanthone, dimethyl thioxanthones, diethyl thioxanthone, diisopropyl thioxanthones, dimethylamino methyl benzoic ether, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, methyl benzoylformate, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone, 2; Two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-; 3,5-s-triazine, 2,4; 6-three (trichloromethyl)-1; 3,5-s-triazine, 2, two (the trisbromomethyl)-6-(4 '-methoxyphenyl)-1 of 4-; 3; 5-s-triazine, 2,4,6-three (trisbromomethyl)-1; 3; 5-s-triazine, 2, two (the trichloromethyl)-6-(1,3-benzo dioxolanes-5-yl)-1 of 4-; 3; 5-s-triazine, benzophenone, benzoylbenzoic acid, 1-(4-phenyl sulfenyl phenyl) butane-1,2-diketone-2-oxime-O-benzoic ether, 1-(4-methyl sulfenyl phenyl) butane-1,2-diketone-2-oxime-O-acetic acid esters, 1-(4-methyl sulfenyl phenyl) butane-1-ketoxime-O-acetic acid esters, 4; 4 '-two (diethylamino) benzophenone, p-(dimethylamino)-benzoic acid isopentyl ester, (dimethylamino)-ethyl benzoate, 2; 2 '-two (O-chlorphenyl)-4,4 ', 5; 5 '-tetraphenyl-1,2 '-bisglyoxaline, diazo naphthoquinone series initiators and commercially available Kayacure DMBI, Kayacure BDMK, Kayacure BP-100, Kayacure BMBI, Kayacure DETX-S, Kayacure EPA (being Japanese chemical drug manufacturing), Darocure-1173, Darocure-1116 (being Merck Japan makes), Irgacure 907, Irgacure 369 (BASF Japan manufacturing), Irgacure 379EG (BASF Japan manufacturing), Irgacure OXE-01 (BASF Japan manufacturing), Irgacure OXE-02 (BASF Japan manufacturing), Irgacure PAG103 (BASF Japan manufacturing), TME-triazine (Sanwa Chemical manufacturing), bisglyoxaline (dark fund changes into manufacturing), STR-110, STR-1 (being the manufacturing of レ ス ペ ケ ミ カ Le) etc.
Under the situation of the hot curing resin composition that uses in the ink-jet method etc., use thermal polymerization usually, also can share as required with Photoepolymerizationinitiater initiater.As thermal polymerization; The thermal polymerization that azo based compound, organic peroxide system are arranged; For example can enumerate 2,2 '-azoisobutyronitrile, 2,2 '-azo two (2; The 4-methyl pentane nitrile), 2,2 '-azo two (2-methylbutyronitrile), di-tert-butyl peroxide, dibenzoyl peroxide, peroxidating neodecanoic acid cumyl ester etc.
These initiating agents can use more than 2 kinds as required alone or in combination.When the solid constituent of pigmentary resin property composition was made as 100 mass parts, the content of these initiating agents was 0.5～50 mass parts, is preferably 1～25 mass parts.
Be used for organic solvent of the present invention and can use such solvent: this solvent is for having sufficient dissolving power as the resin glue of the constituent of colored resin composition, photopolymerization monomer, Photoepolymerizationinitiater initiater etc., and also has sufficient dissolving power for the synthetic monofunctional monomer that is used for resin glue, polymerization initiator etc.In addition, can use the solvent that when making pigment dispersion, also can keep dispersion stabilization.
Can use as long as be used for organic solvent of the present invention, not special restriction as object lesson, can be enumerated benzene classes such as benzene,toluene,xylene; Cellosolve classes such as methyl cellosolve, ethyl cellosolve, butyl cellosolve; Cellosolve acetate esters such as methylcellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate; Propylene-glycol monoalky lether acetate esters such as propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetic acid esters; Propionic acid esters such as methoxypropionic acid methyl esters, methoxy propyl acetoacetic ester, ethoxy-propionic acid methyl esters, ethoxyl ethyl propionate; Lactic acid esters such as methyl lactate, ethyl lactate, butyl lactate; Diglycol such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether class; Acetate esters such as methyl acetate, ethyl acetate, butyl acetate; Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, dioxane; Ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, cyclohexanone; Alcohols such as methyl alcohol, ethanol, butanols, isopropyl alcohol, phenmethylol, etc.
They can separately or make up more than 2 kinds and use.In addition, with respect to the total solid composition of 100 mass parts colored resin compositions, the consumption of organic solvent is preferably 40～10000 mass parts, more preferably 100～1000 mass parts.
Colored resin composition of the present invention is made through utilizing mixing such as dissolver or homomixer to stir above-mentioned resin glue, hardening agent, specific colorant compounds, organic solvent etc.In addition, can also add other pigment, dyestuff as required, under the situation for the low dyestuff of pigment or dissolubility, use suitable spreading agent to obtain dispersion, join in the colored resin composition and mix through dispersion machines such as coating rockers.
Colored resin composition of the present invention can also add various adjuvants as required, for example filling agent, surfactant, Photoepolymerizationinitiater initiater, thermal polymerization, polymerization inhibitor, driving fit promoter, anti-oxidant, ultraviolet light absorber, anti-polycoagulant etc.In addition, colored resin composition of the present invention is in order to remove foreign matter etc. in its preparation back, can also utilize filtrator etc. to carry out micro porous filtration.
Next, describe for method by its solidfied material of colored resin composition preparation of the present invention.At first; Utilizing spin-coating method, rolling method, slit and method of spin coating, mould to be coated with methods such as method, excellent Tu Fa is applied to colored resin composition of the present invention on the substrates such as glass substrate, silicon substrate; Make thickness be about 0.1～20 μ m, 0.5～5 μ m more preferably; As required; In decompression chamber, with temperature 23～150 ℃ of 1～60 minute following time, more preferably the drying condition of 60～120 ℃ of 1～10 minute following times of temperature carries out drying under reduced pressure, and then utilize heating plate or cleaning oven etc. to carry out pre-bake treatment, thus the system film.Then, utilize general photolithography to see through predetermined mask patterned illumination radioactive ray and (can enumerate for example electron ray, ultraviolet ray, preferred ultraviolet ray.), utilize the mixed aqueous solution of water phase surfactant mixture, alkaline aqueous solution or surfactant and alkaline reagent to develop.Visualization way has infusion process, spray-on process, shower method, puddles method, ultrasound wave development method etc., also can in them any be made up.Remove not illuminated portion through development; With curing processing behind the laggard row of water rinse; For example handle with under 130～300 ℃ of the temperature, 1～120 minute time, more preferably under 150～250 ℃ of the temperature, the condition of 1～30 minute time carries out, thereby obtain the pixel that constitutes by color solidification film of the present invention.
Among above-mentioned,, can use polyoxyethylene alkyl ether, polyoxyalkylene alkyl etc. as surfactant.In addition, as alkaline reagent, use sodium carbonate, sal tartari, NaOH, potassium hydroxide, diethanolamine, TMAH etc.Among the present invention, the preferred use contained the two the WS of alkaline reagent and surfactant.Develop usually 10～50 ℃, be preferably under 20～40 ℃ the treatment temperature common 30～600 seconds, processing time of being preferably 30～120 seconds to carry out.
The solidfied material of colored resin composition of the present invention as be suitable for liquid crystal indicator, organic el panel, or to be used for the color filter of solid state image sensor etc. of digital camera etc. useful; This color filter has a kind of pixel, and this pixel is the patterned pixel that the solidfied material by colored resin composition of the present invention for preparing as stated constitutes.
In the display device of the present invention, liquid crystal indicator is the structure fabrication so that lamination such as backlight, polarizing coating, show electrode, liquid crystal, alignment films, common electrode, color filter of the present invention, polarizing coating etc. are successively formed for example.Organic el panel through on the multilayer organic illuminating element or under arbitrary square one-tenth color filter of the present invention make.In addition,, for example, color-filter layer of the present invention is set on the silicon wafer of electrode, photodiode being provided with to pass on about solid state image sensor, then lamination lenticule, thus make.
Embodiment
Illustrate in greater detail the present invention through following examples, but the present invention is not limited to these embodiment.In addition,, utilize spectrophotometer " UV-3150 of Shimadzu Seisakusho Ltd. " to measure spectral transmission, calculate the colourity in the XYZ colorimeter system, the patience of tingle body is estimated about dichroism.
Synthetic example 1
In the 100ml beaker, feed intake rhodamine B (Tokyo change into industry make) 1g, the water 20g of following formula (100) stirred 30 minutes at normal temperatures.To wherein dripping the solution that the cesium salt 1g that in DMF 1g, dissolves three (trifluoromethane sulfonyl group) methide (TFSM) forms, stirred 3 hours.With the dye filtering of separating out, washing, drying, obtain as the compound N of the TFSM salt of rhodamine B 0.7g o.1.Maximum absorption wavelength: 560nm (cyclohexanone)
Synthetic example 2
In the 100ml beaker, feed intake rhodamine 6G (Tokyo change into industry make) 1g, the water 20g of following formula (101) stirred 30 minutes at normal temperatures.To wherein dripping the solution that the cesium salt 1g that in DMF 1g, dissolves three (trifluoromethane sulfonyl group) methide forms, stirred 3 hours.With the dye filtering of separating out, washing, drying, obtain as the compound N of the TFSM salt of rhodamine 6G 0.8g o.2.Maximum absorption wavelength: 531nm (cyclohexanone)
3 (preparations of resin glue (multipolymer)) of synthetic example
In the four-hole boiling flask of 500ml, feed intake methyl ethyl ketone 160g, methacrylic acid 10g, benzyl methacrylate 33g, α, α '-azo two (isobutyronotrile) 1g flows into nitrogen 30 minutes while stir in flask.Thereafter, be warming up to 80 ℃, the state that remains on 80～85 ℃ stirred 4 hours down.Behind the reaction terminating, be cooled to room temperature, obtain water white transparency and uniform copolymer solution.It is precipitated in 1: 1 mixed solution of isopropyl alcohol and water, and filter,, obtain multipolymer (A) solid constituent taking-up, drying.The polystyrene conversion weight-average molecular weight of resulting multipolymer (A) is 18000, and acid number is 152.
Embodiment 1
Will as multipolymer (A) 5.4g of resin glue, as KAYARAD DPHA (the Japanese chemical drug manufacturing) 6g of photopolymerization monomer, as Irgacure 907 (the BASF Japan manufacturing) 1.5g of Photoepolymerizationinitiater initiater and Kayacure DETX-S (Japanese chemical drug manufacturing) 0.6g, as synthetic routine 1 compound N of dyestuff o.1 0.6g, mix respectively as the cyclohexanone 20g and the propylene glycol methyl ether acetate 8.6g of solvent, obtain the colored resin composition of purple of the present invention.
Embodiment 2～3 is described below.
Embodiment 2: except will synthesize compound N that o.1 example 1 compound N change to synthetic example 2 o.2, forms identically with embodiment 1, obtain the colored resin composition of redness.
Embodiment 3: after the ratio of components mixing with C.I. pigment blue 15: 6/AJISPER PB821/Solsperse 5000/PGMEA=15.0/6.0/1.0/78.0 (mass ratio); Add 0.3mm zirconium oxide bead 400g; Carry out handling in 60 minutes with the coating rocker, and filter, thereby obtain dispersible pigment dispersion 1.In embodiment 1, add 19g dispersible pigment dispersion 1, obtain colored resin composition of the present invention.
Comparative example 1: o.1 change to the rhodamine B except synthesizing example 1 compound N, form identically, obtain the colored resin composition of purple with embodiment 1.
Comparative example 2: o.1 change to the rhodamine 6G except synthesizing example 1 compound N, forms identically, obtain the colored resin composition of redness with embodiment 1.
Comparative example 3: o.1 change to the Basic Blue 7 except synthesizing example 1 compound N, forms identically, obtain the colored resin composition of blueness with embodiment 1.
Patterning is estimated
The above-mentioned colored resin composition that obtains (embodiment 1～3) is applied on the aforesaid substrate; After carrying out prebake with 80 ℃ * 100 seconds condition; Solidify across mask utilization exposure, develop with the alkaline aqueous solution that contains surfactant then, and with behind the water rinse; With 200 ℃ of heating, obtain colored pattern.Resulting colored pattern has the square resolution of 5 μ m in line &space, does not confirm to peeling off of residue, pixel etc.
About the thermotolerance evaluation
With above-mentioned each composition of coating on glass substrate likewise, to carry out blanket exposure, and cure processing after carrying out (200 ℃ * 5 minutes), making is used to estimate stable on heating substrate.According to the following stated carry out various evaluations thereafter.About thermotolerance, utilize the transmissivity of spectrophotometric determination evaluation with substrate, next after 120 minutes, measure spectral transmission once more 200 ℃ of processing, calculate aberration (Δ Eab), thereby carry out the thermotolerance evaluation.Stable on heating result lists in table 2.
[table 2]
The stable on heating evaluation result of table 2
| ΔEab | |
| Embodiment 1 | 0.2 |
| Embodiment 2 | 0.6 |
| Embodiment 3 | 3.5 |
| Comparative example 1 | - |
| Comparative example 2 | 37.4 |
| Comparative example 3 | 58.7 |
In the comparative example 1, cure the colour killing of confirming pigment in the processing after before heat-resisting processing, formed significantly relatively poor result of thermotolerance.
Table 2 is stable on heating evaluation result, compares with the dyestuff of comparative example 2 and 3 existing type, and the thermotolerance of embodiments of the invention 1～3 significantly improves.Embodiment 3 has share pigment, even but the colorant compounds of the present invention that will have various chromatic characteristics such as blueness, redness mix with pigment, embodiment 3 does not have special separating out yet, and demonstrates good result.
In sum, the present invention can form color filter through the colored resin composition that has used specific colorant compounds, though resulting color filter is a dyestuff, has sufficient patience, therefore can access distinct pixel high-quality, high reliability.In addition, also can mix well according to purposes and to use, can know in industry, to have very high value with pigment, other dyestuffs.
Claims (7)
1. a color filter is used colored resin composition, and it contains colorant compounds, resin glue, solvent, the hardening agent of following formula (1) expression,
In the formula (1), R
1～R
6Alkyl, the alkoxy of C1-C12, nitro, carboxyl, the alkoxy carbonyl of representing hydrogen atom, halogen atom, C1-C12 independently of one another, Y
1～Y
4Alkyl, the aryl of representing hydrogen atom, C1-C12 independently of one another, X
1～X
5Alkyl, the alkoxy of C1-C12, halogen atom, nitro, phenoxy group, carboxyl, alkoxy carbonyl, carbamyl, sulfo group, the sulfamoyl of representing hydrogen atom, C1-C12 independently of one another, anionicsite Z
-Expression has the sulfonyl methide negative ion of the high halogenated alkyl of C1-C10.
2. color filter as claimed in claim 1 is used colored resin composition, wherein, and the Z in the formula (1)
-It is three (trifluoromethane sulfonyl group) methide negative ion.
3. according to claim 1 or claim 2 colored resin composition, it contains metal phthalocyanine pigment.
4. a color filter is used the color solidification film, and it carries out patterning through each the described colored resin composition that uses claim 1～3 and forms.
5. color filter, it is processed with the color solidification film by the described color filter of claim 4.
6. display device, it is equipped with the described color filter of claim 5 and forms.
7. solid state image sensor, it is equipped with the described color filter of claim 5 and forms.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-135702 | 2010-06-15 | ||
| JP2010135702 | 2010-06-15 | ||
| JP2010151004 | 2010-07-01 | ||
| JP2010-151004 | 2010-07-01 | ||
| JP2010243009 | 2010-10-29 | ||
| JP2010-243009 | 2010-10-29 | ||
| PCT/JP2011/063353 WO2011158748A1 (en) | 2010-06-15 | 2011-06-10 | Colored resin composition, colored cured film, color filter, display device and solid-state image sensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102472852A true CN102472852A (en) | 2012-05-23 |
Family
ID=45348148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800030317A Pending CN102472852A (en) | 2010-06-15 | 2011-06-10 | Colored resin composition, colored cured film, color filter, display device and solid-state image sensor |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP5750045B2 (en) |
| KR (1) | KR20130048129A (en) |
| CN (1) | CN102472852A (en) |
| SG (1) | SG178428A1 (en) |
| TW (1) | TW201209045A (en) |
| WO (1) | WO2011158748A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102346370A (en) * | 2010-07-30 | 2012-02-08 | Jsr株式会社 | Coloring composition, color filter and display element |
| CN105842984A (en) * | 2015-01-30 | 2016-08-10 | 住友化学株式会社 | Coloring photosensitive resin composition |
| CN106104379A (en) * | 2014-05-21 | 2016-11-09 | 三星Sdi株式会社 | Photosensitive resin composition and use its colored filter |
| CN102346370B (en) * | 2010-07-30 | 2016-12-14 | Jsr株式会社 | Coloured composition, color filter and display element |
| CN107759557A (en) * | 2016-08-19 | 2018-03-06 | 株式会社Lg化学 | Compound, the colorant composition containing it and the resin combination containing it |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5932435B2 (en) * | 2012-03-29 | 2016-06-08 | サカタインクス株式会社 | Blue pigment dispersion composition for color filter and blue pigment dispersion resist composition for color filter containing the same |
| KR101361679B1 (en) * | 2012-03-30 | 2014-02-12 | (주)경인양행 | Xanthene dye compounds, colored resin composition comprising the same for color filter and color filter using the same |
| JP6162084B2 (en) * | 2013-09-06 | 2017-07-12 | 富士フイルム株式会社 | Colored composition, cured film, color filter, method for producing color filter, solid-state imaging device, image display device, polymer, xanthene dye |
| JP6374172B2 (en) | 2014-01-31 | 2018-08-15 | 富士フイルム株式会社 | Colored composition, cured film using the same, color filter, pattern forming method, color filter manufacturing method, solid-state imaging device, image display device, and dye multimer |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005021661A1 (en) * | 2003-08-21 | 2005-03-10 | Merck Patent Gmbh | Cyanoborate, fluoroalkyl phosphate, fluoroalkyl borate or imide dyes |
| JP2008088426A (en) * | 2006-09-06 | 2008-04-17 | Nippon Kayaku Co Ltd | New cyanine compound and use of the same |
| JP2008242311A (en) * | 2007-03-28 | 2008-10-09 | Sumitomo Chemical Co Ltd | Colored photosensitive resin composition, and color filter array using the same, and solid state imaging device |
| JP5504627B2 (en) * | 2008-07-01 | 2014-05-28 | 住友化学株式会社 | Colored photosensitive resin composition |
-
2011
- 2011-06-10 WO PCT/JP2011/063353 patent/WO2011158748A1/en active Application Filing
- 2011-06-10 KR KR1020117024217A patent/KR20130048129A/en not_active Application Discontinuation
- 2011-06-10 SG SG2012010526A patent/SG178428A1/en unknown
- 2011-06-10 JP JP2011538770A patent/JP5750045B2/en not_active Expired - Fee Related
- 2011-06-10 CN CN2011800030317A patent/CN102472852A/en active Pending
- 2011-06-14 TW TW100120751A patent/TW201209045A/en unknown
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102346370A (en) * | 2010-07-30 | 2012-02-08 | Jsr株式会社 | Coloring composition, color filter and display element |
| CN102346370B (en) * | 2010-07-30 | 2016-12-14 | Jsr株式会社 | Coloured composition, color filter and display element |
| CN106104379A (en) * | 2014-05-21 | 2016-11-09 | 三星Sdi株式会社 | Photosensitive resin composition and use its colored filter |
| CN106104379B (en) * | 2014-05-21 | 2019-11-19 | 三星Sdi株式会社 | Photosensitive resin composition and the colored filter for using it |
| CN105842984A (en) * | 2015-01-30 | 2016-08-10 | 住友化学株式会社 | Coloring photosensitive resin composition |
| CN107759557A (en) * | 2016-08-19 | 2018-03-06 | 株式会社Lg化学 | Compound, the colorant composition containing it and the resin combination containing it |
| CN107759557B (en) * | 2016-08-19 | 2021-08-27 | 株式会社Lg化学 | Compound, colorant composition containing the same, and resin composition containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20130048129A (en) | 2013-05-09 |
| WO2011158748A1 (en) | 2011-12-22 |
| SG178428A1 (en) | 2012-03-29 |
| TW201209045A (en) | 2012-03-01 |
| JPWO2011158748A1 (en) | 2013-08-19 |
| JP5750045B2 (en) | 2015-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102472853A (en) | Colored resin composition, colored cured film, color filter, display device, and solid-state imaging element | |
| CN102472851A (en) | Colored resin composition, colored cured film, color filter, display device, and solid-state imaging element | |
| TWI494378B (en) | Red coloring composition for color filter, and color filter | |
| TWI443458B (en) | Red-coloring composition for color filter and color filter | |
| CN102914944A (en) | Colored resin composition | |
| JP6264854B2 (en) | Coloring composition for color filter, and color filter | |
| TWI500711B (en) | Coloring composition for use in color filter and color filter | |
| CN102472852A (en) | Colored resin composition, colored cured film, color filter, display device and solid-state image sensor | |
| CN102472850A (en) | Colored resin composition, colored cured film, color filter, liquid crystal display device, organic el display, and solid-state imaging element | |
| CN103635541A (en) | Dye dispersion, photosensitive resin composition for color filter, color filter, liquid crystal display device, and organoluminescent display device | |
| JPWO2012053201A1 (en) | Colored resin composition for color filter, color filter, display device, and solid-state imaging device | |
| TW201341957A (en) | Radiation-sensitive coloring composition, color filter and display device | |
| WO2013011687A1 (en) | Colored resin composition for color filters | |
| JP2012098522A (en) | Colored resin composition | |
| CN102445847A (en) | Colored photosensitive resin composition, color filter and liquid crystal display | |
| TW201235365A (en) | Colored resin composition | |
| JP5999704B2 (en) | Colored resin composition | |
| JP2012083651A (en) | Colored resin composition | |
| JP5959009B2 (en) | Xanthene compound, colored resin composition | |
| JP4346230B2 (en) | Color filter composition and color filter | |
| TW201229143A (en) | Colored resin composition for color filter and color filter using the composition | |
| JP2015152878A (en) | Colored resin composition for color filter | |
| JP2020111627A (en) | Colored resin composition | |
| JP2012155183A (en) | Colored resin composition | |
| TW202033675A (en) | Coloring composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120523 |