WO2012165537A1 - 着色組成物、カラーフィルタ及び表示素子 - Google Patents
着色組成物、カラーフィルタ及び表示素子 Download PDFInfo
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- WO2012165537A1 WO2012165537A1 PCT/JP2012/064056 JP2012064056W WO2012165537A1 WO 2012165537 A1 WO2012165537 A1 WO 2012165537A1 JP 2012064056 W JP2012064056 W JP 2012064056W WO 2012165537 A1 WO2012165537 A1 WO 2012165537A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
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- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
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- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B55/00—Azomethine dyes
- C09B55/005—Disazomethine dyes
- C09B55/006—Disazomethine dyes containing at least one heteroring
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- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
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- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
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- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
- C09B69/06—Dyestuff salts, e.g. salts of acid dyes with basic dyes of cationic dyes with organic acids or with inorganic complex acids
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- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/103—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a diaryl- or triarylmethane dye
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
Definitions
- the present invention relates to a colored composition, a color filter, and a display element. More specifically, the present invention is suitably used for a color filter such as a transmissive or reflective color liquid crystal display element, a solid-state imaging element, an organic EL display element, and electronic paper.
- a color filter such as a transmissive or reflective color liquid crystal display element, a solid-state imaging element, an organic EL display element, and electronic paper.
- the present invention relates to a colored composition, a color filter including a colored layer formed using the colored composition, and a display element including the color filter.
- a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape.
- a method Patent Documents 1 and 2) in which pixels of each color are obtained by irradiation (hereinafter referred to as “exposure”) and development.
- Exposure irradiation
- development A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (Patent Document 3) is also known.
- Patent Document 4 proposes the use of a triarylmethane compound having a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonylmethide anion.
- the subject of this invention is providing the coloring composition which can manufacture the color filter excellent also in solvent resistance with heat resistance etc. Furthermore, the subject of this invention is providing the display element which comprises the color filter provided with the colored layer formed using the said coloring composition, and the said color filter.
- the present invention is a colored composition containing (A) a colorant, (B) a binder resin, (C) a compound having two or more ethylenically unsaturated groups, and (D) a photopolymerization initiator.
- specific colorant a coloring composition comprising an intermolecular hydrogen abstraction type photo radical initiator as a photo polymerization initiator is provided.
- the present invention also provides a color filter comprising a colored layer formed using the colored composition, and a display element comprising the color filter.
- the “colored layer” means each color pixel, black matrix, black spacer, etc. used in the color filter.
- the colored composition of the present invention is used, a colored layer having excellent solvent resistance as well as heat resistance can be formed. Therefore, the colored composition of the present invention is used for various color filters including color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It can be used very suitably for production.
- the coloring composition of the present invention is a basic coloring having, as a coloring agent, a specific coloring agent, that is, an anion having at least one electron-withdrawing group selected from the group consisting of a cyano group, a halogenated hydrocarbon group, and a halosulfonyl group. It contains an agent.
- the basic colorant is an ionic colorant having a cation moiety as a chromophore, preferably a basic dye.
- the specific colorant can be used alone or in admixture of two or more.
- the anion moiety in the specific colorant is not particularly limited as long as it is an anion having at least one electron-withdrawing group selected from the group consisting of a cyano group, a halogenated hydrocarbon group, and a halosulfonyl group.
- Examples include anions represented by the following formulas (1a) to (1e).
- R 1 represents a halogenated hydrocarbon group which may have a linking group, and a represents an integer of 1 or more.
- R 2 independently represents a halogenated alkylsulfonyl group which may have a cyano group, a halosulfonyl group or a linking group, and R 2 has a linking group. Or a halogenated alkylsulfonyl group, R 2 may be bonded to each other to form a ring.
- R 3 represents a halogenated hydrocarbon group which may have a linking group
- P represents a phosphorus atom
- Hal represents a halo group
- b represents an integer of 1 to 6.
- R 4 represents a halogenated hydrocarbon group or a cyano group which may have a linking group
- B represents a boron atom
- Hal represents a halo group
- R 4 and Hal each represents When there are a plurality, they may be the same or different.
- c represents an integer of 1 to 4.
- R 5 are independently of each other, showing a halosulfonyl group or a halogenated alkylsulfonyl group.
- examples of the hydrocarbon group forming the skeleton of the halogenated hydrocarbon group of R 1 , R 3 and R 4 include ( i) an aliphatic hydrocarbon group, (ii) an alicyclic hydrocarbon group, (iii) an aliphatic hydrocarbon group having an alicyclic hydrocarbon group as a substituent (hereinafter referred to as “alicyclic hydrocarbon-substituted aliphatic carbonization”).
- a hydrogen group ”), (iv) an aromatic hydrocarbon group, (v) an aromatic hydrocarbon group having an aliphatic hydrocarbon group as a substituent (hereinafter referred to as an“ aliphatic hydrocarbon-substituted aromatic hydrocarbon group ”) And (vi) an aliphatic hydrocarbon group having an aromatic hydrocarbon group (hereinafter referred to as “aromatic hydrocarbon-substituted aliphatic hydrocarbon group”) and the like.
- the hydrocarbon group constituting the skeleton of R 1 , R 3 and R 4 is preferably the following characteristic group from the viewpoint of solubility in an organic solvent.
- the aliphatic hydrocarbon group is preferably an alkyl group, which may be linear or branched.
- the number of carbon atoms of the aliphatic hydrocarbon group is preferably 1-20, particularly 1-8. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
- the alicyclic hydrocarbon group is preferably an alicyclic saturated hydrocarbon group, and the carbon number thereof is preferably 3 to 20, particularly 3 to 12.
- the alicyclic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an alicyclic saturated hydrocarbon-substituted alkyl group, and the alkyl group may be linear or branched.
- the number of carbon atoms of the alicyclic hydrocarbon-substituted aliphatic hydrocarbon group is preferably 4 to 20, particularly 6 to 14.
- Specific examples include a cyclohexylmethyl group and a cyclohexylethyl group.
- the aromatic hydrocarbon group preferably has 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms. Specific examples include a phenyl group and a naphthyl group.
- the aliphatic hydrocarbon-substituted aromatic hydrocarbon group is preferably an alkyl-substituted phenyl group, and the alkyl moiety may be linear or branched.
- the number of carbon atoms of the aliphatic hydrocarbon-substituted aromatic hydrocarbon group is preferably 7 to 30, particularly 7 to 20. Specific examples include a tolyl group, a xylyl group, an ethylphenyl group, an isopropylphenyl group, and a nonylphenyl group.
- the aromatic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an aralkyl group, and the carbon number thereof is preferably 7 to 30, particularly 7 to 20. Specific examples include a benzyl group and a phenethyl group.
- the hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group includes (i) an aliphatic hydrocarbon group, (iii) an alicyclic hydrocarbon-substituted aliphatic hydrocarbon group, and (iv) an aromatic hydrocarbon.
- a phenyl group and an aralkyl group are more preferable, and an alkyl group is particularly preferable.
- the halogen in the halogenated hydrocarbon group is preferably fluorine from the viewpoint of the heat resistance of the colorant.
- fluorine By selecting fluorine as a substituent, the anion part of the colorant becomes a conjugate base of an organic acid with a higher acidity, and thus a salt with a stronger ionic bond is formed and heat resistance is improved. It is done.
- Examples of the linking group in the halogenated hydrocarbon group of R 1 , R 3 and R 4 and the halogenated alkylsulfonyl group of R 2 include —O—, —S—, —CO—, —COO—, —CONH— , —SO 2 — and the like.
- the carbon number referred to in paragraph [0023] means the total carbon number of the portion excluding the carbon atoms constituting the linking group.
- R 1 , R 3 and R 4 are preferably groups represented by the following formula (1-1) or (1-2). Particularly preferred is a group represented by the following formula (1-1) which forms a conjugated base of a strong organic acid.
- R 19 represents a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, an alicyclic hydrocarbon group, an alkoxy group, a fluorinated alkoxy group, R 20 COOR 21 — or R 20 COOR. 21 CFH— (R 20 represents an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or a substituted or unsubstituted aryl group, R 21 represents an alkanediyl group), and n is an integer of 1 or more “*” Indicates a bond. ]
- R 22 to R 26 each independently represent a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluorinated alkyl group or an alkoxy group, and “*” is a bond. It shows that. However, at least one of R 22 to R 26 is a fluorine atom or a fluorinated alkyl group.
- the alkyl group, fluorinated alkyl group, alkoxy group and fluorinated alkoxy group preferably have 1 to 16, more preferably 1 to 12, and more preferably 1 to 8 carbon atoms.
- the alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms, more preferably 3 to 7 carbon atoms.
- R 19 is preferably a fluorine atom, a fluorinated alkyl group, an alicyclic hydrocarbon group, a fluorinated alkoxy group, R 20 COOR 21 — or R 20 COOR 21 CFH—.
- An alicyclic hydrocarbon group, a perfluoroalkoxy group, R 20 COOCH 2 CH 2 — or R 20 COOCH 2 CH 2 CFH— is particularly preferable.
- R 20 represents an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group, or a substituted or unsubstituted aryl group.
- the alkyl group may be linear or branched, and the alkyl group has 1 to 12 carbon atoms.
- the alicyclic hydrocarbon group may be a 2- to 4-ring bridged alicyclic hydrocarbon group, and the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.
- the heteroaryl group is preferably a group composed of a 5- to 10-membered aromatic heterocycle containing one or more heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom.
- the aryl group is preferably an aryl group having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably a phenyl group.
- substituents examples include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halo group, and a trifluoromethyl group.
- the position and number of the substituent are arbitrary, and In the case of having two or more groups, the substituents may be the same or different.
- R 21 represents an alkanediyl group, preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
- methylene group ethylene group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2 , 2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4-diyl group, pentane-1,5-diyl group Hexane-1,5-diyl group, hexane-1,6-diyl group and the like.
- an ethylene group is preferable from the viewpoint of ease of production.
- 10 is preferable and the upper limit of n is more preferable.
- at least three of R 22 to R 26 are preferably fluorine atoms or fluorinated alkyl groups.
- the alkyl group constituting the skeleton of the halogenated alkylsulfonyl group of R 2 and R 5 may be linear or branched, and preferably has 1 to 8 carbon atoms.
- Specific examples of the alkyl group include the same alkyl groups as those in the halogenated hydrocarbon group.
- the halo group in the halogenated alkylsulfonyl group is preferably a fluoro group.
- the halogenated alkylsulfonyl group is preferably a perfluoroalkylsulfonyl group, for example, a CF 3 SO 2 group, a CF 3 CF 2 SO 2 group, a (CF 3 ) 2 CFSO 2 group, or a CF 3 CF 2 CF 2 SO 2 group.
- a CF 3 SO 2 group is preferable.
- the anion represented by the above formula (1a) is an anion in which a halogenated hydrocarbon group of R 1 is substituted with a number of SO 3 - groups, and a is preferably an integer of 1 to 4, particularly preferably 1 or 2. preferable.
- the halogenated hydrocarbon group of R 1 can be a monovalent to tetravalent halogenated hydrocarbon group, and the divalent to tetravalent halogenated hydrocarbon group has the skeleton of the aforementioned halogenated hydrocarbon group. Examples thereof include residues obtained by removing 1 to 3 hydrogen atoms from the hydrocarbon groups (i) to (vi) exemplified in the formed hydrocarbon group.
- Specific examples of preferred anions represented by the above formula (1a) include anions represented by the following formula (1a-1) or (1a-2).
- R 1a represents a monovalent halogenated hydrocarbon group which may have a linking group.
- R 1b represents a halogenated alkanediyl group which may have a linking group.
- Representative examples of the anion represented by the above formula (1a-1) include anions shown in the following compound group a and compound group b.
- anion represented by the formula (1b) include, for example, [(CN) 2 N] ⁇ , [(FSO 2 ) 2 N] ⁇ , [(FSO) in addition to the anions shown in the following compound group d. 2 ) N (CF 3 SO 2 )] ⁇ , [(FSO 2 ) N (CF 3 CF 2 SO 2 )] ⁇ , [(FSO 2 ) N ⁇ (CF 3 ) 2 CFSO 2 ⁇ ] ⁇ , [(FSO 2 ) N (CF 3 CF 2 CF 2 SO 2 )] ⁇ , [(FSO 2 ) N (CF 3 CF 2 CF 2 SO 2 )] ⁇ , [(FSO 2 ) N (CF 3 CF 2 CF 2 SO 2 )] ⁇ , [(FSO 2 ) N ⁇ (CF 3 ) 2 CFCF 2 SO 2 ⁇ ] ⁇ , [(FSO 2 ) N ⁇ CF 3 ) 2 CFCF 2 SO 2
- Representative examples of the anion represented by the above formula (1c) include, for example, (CF 3 ) 3 PF 3 ⁇ , (C 2 F 5 ) 2 PF 4 ⁇ , (C 2 F 5 ) 3 PF 3 ⁇ , [ (CF 3 ) 2 CF] 2 PF 4 ⁇ , [(CF 3 ) 2 CF] 3 PF 3 , (nC 3 F 7 ) 2 PF 4 ⁇ , (nC 3 F 7 ) 3 PF 3 ⁇ , (N-C 4 F 9 ) 3 PF 3 ⁇ , (C 2 F 5 ) (CF 3 ) 2 PF 3 ⁇ , [(CF 3 ) 2 CFCF 2 ] 2 PF 4 ⁇ , [(CF 3 ) 2 CFCF 2 ] 3 PF 3 ⁇ , (nC 4 F 9 ) 2 PF 4 ⁇ , (nC 4 F 9 ) 3 PF 3 ⁇ , (C 2 F 4 H) (CF 3 ) 2 PF
- anion represented by the above formula (1d) include, for example, (CF 3 ) 4 B ⁇ , (CF 3 ) 3 BF ⁇ , (CF 3 ) 2 BF 2 ⁇ , (CF 3 ) BF 3 ⁇ , (C 2 F 5 ) 4 B ⁇ , (C 2 F 5 ) 3 BF ⁇ , (C 2 F 5 ) BF 3 ⁇ , (C 2 F 5 ) 2 BF 2 ⁇ , (CF 3 ) (C 2 F 5 ) 2 BF ⁇ , (C 6 F 5 ) 4 B ⁇ , [(CF 3 ) 2 C 6 H 3 ] 4 B ⁇ , (CF 3 C 6 H 4 ) 4 B ⁇ , (C 6 F 5 ) 2 BF 2 ⁇ , (C 6 F 5 ) BF 3 ⁇ , (C 6 H 3 F 2 ) 4 B ⁇ , B (CN) 4 ⁇ , B (CN) F 3 ⁇ , B (CN) 4
- B (CN) 4 ⁇ , B (CN) F 3 ⁇ , B (CN) 2 F 2 ⁇ , B (CN) 3 F ⁇ , (CF 3 ) 4 B ⁇ , (C 6 F 5 ) 4 B - , [(CF 3 ) 2 C 6 H 3 ] 4 B - are preferred.
- Representative examples of the anion represented by the above formula (1e) include, for example, (CF 3 SO 2 ) 3 C ⁇ , (CF 3 CF 2 SO 2 ) 3 C ⁇ , [(CF 3 ) 2 CFSO 2 ] 3 C ⁇ , (CF 3 CF 2 CF 2 SO 2 ) 3 C ⁇ , (CF 3 CF 2 CF 2 SO 2 ) 3 C ⁇ , [(CF 3 ) 2 CFCF 2 SO 2 ] 3 C ⁇ , [CF 3 CF 2 (CF 3 ) CFSO 2 ] 3 C ⁇ , [(CF 3 ) 3 CSO 2 ] 3 C ⁇ , (FSO 2 ) 3 C ⁇ , (ClSO 2 ) 3 C ⁇ , (BrSO 2 ) 3 C ⁇ , (ISO 2) 3 C - and the like. Of these, (CF 3 SO 2 ) 3 C - is preferable.
- the specific colorant is not particularly limited as long as it is a basic colorant having the above-mentioned specific anion part.
- Coloring agents, cyanine coloring agents, methine coloring agents and the like can be mentioned.
- xanthene-based colorants and triarylmethane-based colorants are preferable.
- the use of triarylmethane-based colorants together with an intermolecular hydrogen abstraction type photoradical initiator makes the desired effect more remarkable. It is preferable at the point obtained.
- the triarylmethane colorant those having a cation represented by the following formula (2) are preferable.
- the resonance structure is equivalent to the cation represented by the following formula.
- a resonance structure exists also about the cation represented by each formula, it shall be equivalent to the cation represented by the said formula.
- R 6 and R 7 each independently represent a hydrogen atom, a linear or cyclic alkyl group having 1 to 8 carbon atoms, a phenyl group or a group having an ethylenically unsaturated bond
- R 8 and R 9 each independently represent a hydrogen atom, a linear or cyclic alkyl group having 1 to 8 carbon atoms, a phenyl group or a group having an ethylenically unsaturated bond
- R 10 represents a hydrogen atom, a chlorine atom, a chain or cyclic alkyl group having 1 to 8 carbon atoms, or —COOR 17 (R 17 represents a hydrogen atom or a chain or cyclic alkyl group having 1 to 8 carbon atoms).
- R 11 and 14 each independently represent a hydrogen atom, a linear or cyclic alkyl group having 1 to 8 carbon atoms, or R 11 and R 14 together represent a sulfur atom
- R 12 and R 13 each independently represent a hydrogen atom, a chlorine atom or a linear or cyclic alkyl group having 1 to 8 carbon atoms
- Y is a hydrogen atom or the following formula (3);
- R 15 and R 16 each independently represent a hydrogen atom, a linear or cyclic alkyl group having 1 to 8 carbon atoms, a phenyl group, or a group having an ethylenically unsaturated bond.
- an arene ring having 6 to 20 carbon atoms and more preferably 6 to 10 carbon atoms is preferable, and specific examples include a benzene ring, a naphthalene ring, a biphenyl ring, and an anthracene ring.
- R 6 ⁇ R 14 (including the R 17 in -COOR 17), as a chain or cyclic alkyl group of R 15 and R 16 having 1 to 8 carbon atoms in the methyl group, an ethyl group, a propyl group, an isopropyl group, Cyclopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, cyclobutyl group, amyl group, tert-amyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, cycloheptyl group, octyl group, Examples thereof include an isooctyl group, a tertiary octyl group, and a 2-ethylhexyl group.
- the group having an ethylenically unsaturated bond in R 6 to R 9 , R 15 and R 16 is not particularly limited.
- R 18 is the number of carbon atoms) 1 to 4 alkanediyl groups, and Ph represents a phenylene group).
- the alkanediyl group having 1 to 4 carbon atoms in R 18 include a methylene group, an ethylene group, a trimethylene group, a propylene group, and a tetramethylene group.
- a cation represented by the following formula (4) is particularly preferable from the viewpoint of improving luminance and color purity.
- a linear or cyclic alkyl group having 1 to 8, more preferably 1 to 6, or a phenyl group is preferable.
- R 9 a linear or cyclic alkyl group having 1 to 8 carbon atoms and further 1 to 6 carbon atoms or a hydrogen atom is preferable. preferable.
- Examples of the colorant other than the triarylmethane colorant include, for example, a methine colorant having a cation described in Formula (I) of JP2010-209191A, and Formula (1) of JP2010-244027A. And xanthene-based colorants having a cation as described above.
- the specific colorant can be produced by a known method.
- the specific colorant can be produced with reference to JP-T-2007-503477, International Publication No. 2010/123071, etc.
- the specific colorant is, for example, a triarylmethane dye, it exhibits a blue to red color when dissolved in an organic solvent. Therefore, by using the compound alone or in combination with other colorants as appropriate, for example, it can be applied to a colored composition for forming a blue pixel, a red pixel, and a black colored layer.
- the compounds can be used alone or in appropriate mixture with other colorants, for example, blue pixels, red
- the present invention can be applied to a coloring composition for forming a pixel and a black colored layer.
- colors and materials can be appropriately selected according to applications. Specifically, any of pigments, dyes and natural pigments can be used. However, since the color layer constituting the color filter is required to have high color purity, luminance, contrast, light shielding properties, etc. It is preferable to use at least one selected from dyes.
- the pigment may be either an organic pigment or an inorganic pigment, and examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyer's and Colorists). . Specific examples include those with the following color index (CI) names.
- CI color index
- the inorganic pigment examples include, for example, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, and chromium oxide.
- examples include green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.
- the pigment when a pigment is used as another colorant, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.
- the pigment surface may be used by modifying the particle surface with a resin if desired.
- the resin that modifies the pigment particle surface include a vehicle resin described in JP-A No. 2001-108817, or various commercially available resins for dispersing pigments.
- a resin coating method on the carbon black surface for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969, and the like can be employed.
- the organic pigment may be used after the primary particles are refined by so-called salt milling.
- a salt milling method for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.
- the dye can be appropriately selected from various oil-soluble dyes, direct dyes, acid dyes, metal complex dyes, and the like.
- CI color index
- colorants can be used alone or in admixture of two or more.
- the total content of the specific colorant and other colorants used as required is usually in the solid content of the color composition from the viewpoint of forming a pixel having high luminance and excellent color purity, or a black matrix having excellent light shielding properties. 5 to 70% by mass, preferably 5 to 60% by mass. Solid content here is components other than the solvent mentioned later. In the present invention, when the specific colorant is used in combination with another colorant, the content ratio of the specific colorant is 5 to 80% by mass, further 15 to 70% by mass, and further 30 to 60% by mass in the total colorant. % Is preferred.
- the content ratio of the triarylmethane colorant is 20 to 80% by mass, more preferably 20 to 60% in the total colorant. It is preferable that the content be 30% by mass, more preferably 30-50% by mass.
- a pigment when used as a colorant, it can be used together with a dispersant and a dispersion aid as desired.
- a dispersing agent for example, an appropriate dispersing agent such as a cationic type, an anionic type, or a nonionic type can be used, and a polymer dispersing agent is preferable.
- Such dispersants are commercially available.
- acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK Corporation (BYK) Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (Lubrisol Co., Ltd.) ), Polyethylene imine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), polyester-based dispersant, Azisper PB821, Jisupa PB822, Adisper PB880, Adisper PB881 (or more, Ajinomoto Fine-Techno Co., Ltd.), and the like.
- dispersion aid examples include pigment derivatives, and specific examples include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.
- the contents of the dispersant and the dispersion aid can be appropriately determined within a range that does not impair the object of the present invention.
- Binder resin Although it does not specifically limit as binder resin in this invention, it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). (B1) ”) and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as” unsaturated monomer (b2) ").
- unsaturated monomer (b1) examples include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ⁇ -carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like. These unsaturated monomers (b1) can be used alone or in admixture of two or more.
- unsaturated monomer (b2) for example, N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; Aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-hydroxystyrene, p-hydroxy- ⁇ -methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;
- N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide
- Aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-hydroxystyrene, p-hydroxy- ⁇ -methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;
- Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
- Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane.
- These unsaturated monomers (b2) can be used alone or in admixture of two or more.
- the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass.
- copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.
- a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.
- the binder resin in the present invention has a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC (elution solvent: tetrahydrofuran) is usually 1,000 to 100,000, preferably 3,000 to 50,000. If Mw is too small, the remaining film rate of the resulting coating may decrease, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may deteriorate. Or the pattern shape may be damaged, or dry foreign matter may be easily generated during application by the slit nozzle method.
- Mw polystyrene-equivalent weight average molecular weight measured by GPC (elution solvent: tetrahydrofuran) is usually 1,000 to 100,000, preferably 3,000 to 50,000. If Mw is too small, the remaining film rate of the resulting coating may decrease, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may deteriorate. Or the pattern shape may be damaged, or dry foreign matter may be easily generated during application by the slit nozzle method.
- the ratio (Mw / Mn) of the weight average molecular weight of the binder resin in the present invention to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 1.0 to 5. 0, more preferably 1.0 to 3.0.
- the binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc.
- the structure, Mw, and Mw / Mn can be controlled by the method.
- the binder resins can be used alone or in admixture of two or more.
- the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, with respect to 100 parts by mass in total of the specific coloring compound and other colorants used as required. More preferred is 50 to 400 parts by mass, and still more preferred is 100 to 300 parts by mass. If the content of the binder resin is too small, for example, the alkali developability may be decreased, or the storage stability of the resulting colored composition may be decreased. On the other hand, if the content is too large, the colorant concentration is relatively high. Therefore, it may be difficult to achieve the target color density as a thin film.
- (C) Compound having two or more ethylenically unsaturated groups-
- (C) the compound having two or more ethylenically unsaturated groups is not particularly limited, but a compound having two or more (meth) acryloyl groups is preferred.
- the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a caprolactone-modified polyfunctional ( (Meth) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, hydroxyl-functional (meth) acrylate and polyfunctional isocyanate obtained by reacting with polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid
- the polyfunctional (meth) acrylate which has a carboxyl group obtained by making an anhydride react can be mentioned.
- examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of trivalent or higher aliphatic polyhydroxy compounds.
- Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned.
- Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate.
- acid anhydrides examples include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid.
- acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid.
- dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.
- Examples of the caprolactone-modified polyfunctional (meth) acrylate include the compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955.
- Examples of the polyfunctional (meth) acrylate modified with alkylene oxide include di (meth) acrylate modified with at least one selected from ethylene oxide of bisphenol A and propylene oxide of bisphenol A, ethylene oxide of isocyanuric acid and isocyanuric acid Tri (meth) acrylate modified with at least one selected from propylene oxide, tri (meth) acrylate modified with at least one selected from ethylene oxide of trimethylolpropane and propylene oxide of trimethylolpropane, pentaerythritol Tri (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide of pentaerythritol Modified with at least one selected from tetra (meth) acrylate modified with at least one selected from ethylene oxide of pentaeryth
- polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, polyfunctional urethane (meth) acrylates Polyfunctional (meth) acrylates having a carboxyl group are preferred.
- polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate is a compound obtained by reacting pentaerythritol triacrylate and succinic anhydride, among polyfunctional (meth) acrylates having a carboxyl group, and obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride.
- the compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.
- (C) the compound having two or more ethylenically unsaturated groups may be used alone or in admixture of two or more.
- the content of the compound (C) having two or more ethylenically unsaturated groups is preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (B) binder resin. Parts, more preferably 50 to 300 parts by weight, particularly 80 to 200 parts by weight. In this case, if the content of the compound having two or more ethylenically unsaturated groups is too small, sufficient curability may not be obtained.
- the photopolymerization initiator initiates the polymerization reaction of the compound (C) having two or more ethylenically unsaturated groups by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates a possible active species.
- the colored composition of the present invention is characterized by containing an intermolecular hydrogen abstraction type photoradical initiator as (D) a photopolymerization initiator. Thereby, the coloring composition which can form the colored layer excellent in solvent resistance is obtained.
- intermolecular hydrogen abstraction type photoradical initiator examples include biimidazole compounds, benzophenone compounds, thioxanthone compounds, polynuclear quinone compounds, and the like. Of these, biimidazole compounds are preferred.
- the intermolecular hydrogen abstraction type photoradical initiator can be used alone or in admixture of two or more.
- the biimidazole compound is a compound having at least one skeleton represented by the following formula (5), formula (6) or formula (7).
- 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-Dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole is preferred, in particular, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole. Imidazole is preferred.
- the content of the intermolecular hydrogen abstraction type photoradical initiator is usually 0.01 to 50 parts by mass with respect to 100 parts by mass of the compound (C) having two or more ethylenically unsaturated groups.
- the amount is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass, and still more preferably 10 to 30 parts by mass.
- hydrogen donor means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
- hydrogen donor in the present invention mercaptan compounds, amine compounds and the like defined below are preferable.
- a mercaptan compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ A mercaptan hydrogen donor).
- the amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). , "Amine-based hydrogen donor"). These hydrogen donors can also have a mercapto group and an amino group at the same time.
- the mercaptan hydrogen donor can have one or more benzene rings or heterocyclic rings, or both a benzene ring and a heterocyclic ring. When two or more of these rings are present, a condensed ring may be formed. Further, when the mercaptan-based hydrogen donor has two or more mercapto groups, one or more of the remaining mercapto groups are substituted with an alkyl group, an aralkyl group or an aryl group as long as at least one free mercapto group remains. May be.
- mercaptan-based hydrogen donor may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at a place other than the mercapto group.
- mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto- Examples include mercapto-substituted heterocyclic compounds such as 2,5-dimethylaminopyridine.
- mercapto-substituted benzothiazoles such as 2-mercaptobenzothiazole
- mercapto-substituted benzoxazoles such as 2-mercaptobenzoxazole
- 2-mercaptobenzothiazoles are preferable
- mercapto-substituted benzothiazoles are more preferable
- 2-mercaptobenzothiazole is particularly preferable. Is preferred.
- the amine-based hydrogen donor may have one or more benzene rings or heterocyclic rings, or may have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, a condensed ring may be formed.
- the amine-based hydrogen donor may be such that all amino groups may be primary amino groups, or secondary amino groups in which one or more of the amino groups are substituted with alkyl groups or substituted alkyl groups, or primary amino groups.
- It may be a tertiary amino group, or may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like at a place other than the amino group.
- amine-based hydrogen donors include amino-substituted benzophenones such as 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone; 4-diethylaminoacetophenone, 4-dimethyl Aminopropiophenone, ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like can be mentioned.
- amino-substituted benzophenones such as 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone
- 4-diethylaminoacetophenone 4-dimethyl Aminopropiophenone, ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like can be mentioned.
- amino-substituted benzophenones such as 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) is particularly preferable.
- Benzophenone is preferred.
- the amine-based hydrogen donor has a function as a sensitizer even in the case of a photopolymerization initiator other than a biimidazole compound.
- a hydrogen donor can be used individually or in mixture of 2 or more types.
- the content of the hydrogen donor is preferably 0 with respect to 100 parts by mass of the compound (C) having two or more ethylenically unsaturated groups. .01 to 40 parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass.
- the content of the hydrogen donor with respect to 100 parts by mass of the biimidazole compound is preferably 5 to 60 parts by mass, more preferably 10 to 40 parts by mass.
- an intramolecular bond cleavage type photopolymerization initiator can be used in combination with an intermolecular hydrogen abstraction type photoradical initiator as a photopolymerization initiator.
- the intramolecular bond cleavage type photopolymerization initiator include acetophenone compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, ⁇ -diketone compounds, diazo compounds, and imides. Examples thereof include sulfonate compounds. Of these, at least one selected from the group of acetophenone compounds, triazine compounds, and O-acyloxime compounds is preferable.
- the content ratio of the intermolecular hydrogen abstraction type photoradical initiator is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass in the total photopolymerization initiator from the viewpoint of enhancing a desired effect. % Or more. In addition, although an upper limit is not specifically limited, 90 mass% and 80 mass% are preferable.
- an anionic surfactant can be included to improve the heat resistance thereof.
- the anionic surfactant is not particularly limited, and examples thereof include a carboxylic acid surfactant, a phosphoric acid surfactant, and a sulfonic acid surfactant.
- carboxylic acid surfactant examples include stearic acid monoethanolamine salt, sodium stearate, amine ester of polyetherester acid, and the like.
- phosphoric acid surfactant examples include hydroxyethylene oxide phosphate, sodium salt of hydroxyethylene oxide phosphate, ethylene oxide alkyl phosphate, polyoxyethylene styrenated phenyl ether phosphate, and the like. be able to.
- sulfonic acid surfactant examples include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, triethanolamine salt, ammonium lauryl sulfate, sodium lauryl sulfate, sodium dialkylsulfosuccinate, sodium alkylnaphthalenesulfonate, alkyldiphenyl ether disulfonic acid.
- Examples thereof include sodium, ammonium polyoxyethylene styrenated phenyl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate, ammonium polyoxyethylene nonylpropenyl phenyl ether sulfate, and the like.
- phosphoric acid surfactants and sulfonic acid surfactants are preferred from the viewpoint of enhancing the desired effect.
- phosphoric acid surfactants hydroxyethylene oxide phosphate, ethylene oxide alkyl phosphate, and polyoxyethylene styrenated phenyl ether phosphate are particularly preferable.
- sulfonic acid surfactants alkyl ether ammonium sulfates such as polyoxyethylene alkyl ether ammonium sulfate are particularly preferable, and specific examples thereof include polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate.
- Anionic surfactant can be used individually or in mixture of 2 or more types.
- the content of the anionic surfactant is preferably 5 to 50 parts by mass, particularly preferably 20 to 40 parts by mass with respect to 100 parts by mass of the colorant.
- the coloring composition of the present invention may further contain (C) a crosslinking agent other than the compound having two or more ethylenically unsaturated groups (hereinafter, also simply referred to as “(F) crosslinking agent”). Heat resistance and solvent resistance can be improved.
- (F) cross-linking agent include compounds having two or more epoxy groups, compounds having a total of two or more groups selected from N-methylol groups and N-alkoxymethyl groups, and the like. .
- the compound having two or more epoxy groups is preferably a compound having two or more oxetanyl groups.
- Specific examples thereof include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3, 3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3- Oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3 Ethyl-3-o
- examples of the compound having a total of two or more groups selected from N-methylol groups and N-alkoxymethyl groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure.
- the melamine structure and the benzoguanamine structure are a chemical structure having one or more triazine rings as a basic skeleton, a chemical structure having one or more phenyl-substituted triazine rings as a basic skeleton, and a melamine compound, a benzoguanamine compound or a condensation thereof. It is a concept that includes things. Specific examples of such compounds include compounds represented by the following formulas (8) to (12).
- R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
- the crosslinking agent (F) can be used alone or in admixture of two or more.
- the content of the (F) cross-linking agent is preferably 10 to 500 parts by mass, particularly preferably 30 to 200 parts by mass with respect to 100 parts by mass of the (B) binder resin.
- the (F) crosslinking agent in such a range, the heat resistance and solvent resistance can be further improved.
- the coloring composition of the present invention contains the above components (A) to (D) and other components optionally added, but is usually prepared as a liquid composition by blending a solvent.
- a solvent As the solvent, as long as the components (A) to (D) and other components constituting the colored composition are dispersed or dissolved and do not react with these components and have appropriate volatility, the above-mentioned solvents are appropriately used. You can choose to use.
- Ethylene glycol monomethyl ether Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether,
- Lactic acid alkyl esters such as methyl lactate and ethyl lactate; (Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol; Keto alcohols such as diacetone alcohol;
- Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate; Alkoxycarboxylic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate ; Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Other esters such as -propyl, n-butyl butyrate, methyl pyr
- solvents from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Pioneto acetate n- butyl acetate i- butyl, formic acid n- amyl
- the content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent from the colored composition is 5 to 50 from the viewpoint of the coating property and stability of the obtained colored composition.
- An amount of mass% is preferable, and an amount of 10 to 40 mass% is particularly preferable.
- the coloring composition of this invention can also contain a various additive as needed.
- additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimeth
- the coloring composition of the present invention can be prepared by an appropriate method.
- the specific colorant is a basic dye, it is disclosed in, for example, JP-A-2008-58642, JP-A-2010-132874, etc. It can be prepared by the method that has been described.
- a pigment is used together with a basic dye (specific colorant), as disclosed in JP 2010-132874 A, after passing a dye solution containing the specific colorant through a first filter, it is possible to employ a method in which the dye solution that has passed through the filter is mixed with a separately prepared pigment dispersion or the like, and the resulting colored composition is passed through a second filter.
- a basic dye (specific colorant), the above components (B) to (D), and if necessary, the above components (E) to (F) and additive components are dissolved in the solvent (G) to obtain After the obtained solution is passed through the first filter, the solution that has passed through the first filter is mixed with a separately prepared pigment dispersion, and the resulting colored composition is passed through the second filter.
- a method can also be adopted.
- the dye solution containing the specific colorant is passed through the first filter and then passed through the first filter, the components (B) to (D), and, if necessary, the components (E) to (E)
- the component (F) and the additive component were mixed and dissolved, and the resulting solution was passed through the second filter, and the solution that passed through the second filter was further mixed with a separately prepared pigment dispersion.
- a method of preparing the colored composition by passing it through a third filter can also be adopted.
- the color filter of the present invention comprises a colored layer formed using the colored composition of the present invention.
- a light shielding layer black matrix
- pre-baking is performed to evaporate the solvent, thereby forming a coating film.
- post-baking is performed to form a pixel array in which blue pixel patterns are arranged in a predetermined arrangement.
- each colored radiation-sensitive composition of green or red is used, and each colored radiation-sensitive composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above, so that a green pixel array and red color are obtained.
- a color filter in which pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained.
- the order of forming pixels of each color is not limited to the above.
- any one or more of the blue, green, and red pixel arrays may be a colored layer formed using the colored composition of the present invention.
- a black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method. Using the radiation-sensitive composition, it can be formed in the same manner as in the case of forming the pixel.
- the colored composition of the present invention can also be suitably used for forming such black tricks.
- the substrate used when forming the color filter examples include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
- these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
- an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method may be employed.
- a spin coating method or a slit die coating method it is preferable to employ a spin coating method or a slit die coating method.
- Pre-baking is usually performed by a combination of vacuum drying and heat drying.
- the drying under reduced pressure is usually performed until reaching 50 to 200 Pa.
- the conditions for heat drying are usually about 70 to 110 ° C. and about 1 to 10 minutes.
- the coating thickness is usually 0.6 to 8 ⁇ m, preferably 1.2 to 5 ⁇ m, as the film thickness after drying.
- Examples of the radiation light source used when forming at least one selected from the pixel and the black matrix include, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure.
- Examples of the light source include a lamp light source such as a mercury lamp and a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. Radiation having a wavelength in the range of 190 to 450 nm is preferable.
- the exposure dose of radiation is preferably 10 to 10,000 J / m 2 .
- the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution of 5-diazabicyclo- [4.3.0] -5-nonene or the like is preferable.
- a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like
- a shower development method a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like
- the development conditions are preferably 5 to 300 seconds at room temperature.
- the post-baking conditions are usually 120 to 280 ° C. for about 10 to 60 minutes. From the viewpoint of heat resistance of the specific colorant, the post-baking temperature is preferably 240 ° C. or less, particularly preferably 230 ° C. or less. is there.
- the film thickness of the pixel thus formed is usually 0.5 to 5 ⁇ m, preferably 1 to 3 ⁇ m.
- a method for obtaining pixels of each color by an ink jet method disclosed in Japanese Patent Laid-Open Nos. 7-318723 and 2000-310706 can be employed.
- this method first, a partition having a light shielding function is formed on the surface of the substrate.
- pre-baking is performed to evaporate the solvent.
- this coating film is exposed, it is cured by post-baking to form a blue pixel pattern.
- a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate in the same manner as described above.
- a color filter in which pixel patterns of the three primary colors of red, green and blue are arranged on the substrate is obtained.
- the order of forming pixels of each color is not limited to the above.
- any one or more of the blue, green, and red pixel arrays may be a colored layer formed using the colored composition of the present invention.
- the partition has not only a light shielding function but also a function to prevent the colored thermosetting composition of each color discharged into the compartment from being mixed, so that the black matrix used in the first method described above is used.
- a partition is normally formed using a black radiation sensitive composition.
- the substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.
- a protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering.
- a spacer can be further formed to form a color filter.
- the spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer).
- a colored radiation-sensitive composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for forming such a black spacer. Since the color filter of the present invention thus obtained has extremely high luminance and color purity, it is extremely useful for color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like.
- the display element of the present invention comprises the color filter of the present invention.
- the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.
- the color liquid crystal display element provided with the color filter of the present invention may be a transmissive type or a reflective type, and can have an appropriate structure.
- the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween.
- TFT thin film transistor
- a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed and an ITO (indium oxide doped with tin) electrode or IZO (indium oxide and zinc oxide)
- ITO indium oxide doped with tin
- IZO indium oxide and zinc oxide
- the color liquid crystal display device including the color filter of the present invention can include a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp) and a backlight unit using a white LED as a light source.
- a white LED for example, a white LED that obtains white light by mixing red LED, green LED, and blue LED, a white LED that obtains white light by mixing blue LED, red LED, and green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence
- a white LED that obtains white light by color mixing by combining the body, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.
- the color liquid crystal display device having the color filter of the present invention includes a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, an IPS (In-Planes Switching) type, a VA (Vertical Alignment) type, and an OCB (Optic Optical An appropriate liquid crystal mode such as a birefringence type can be applied.
- TN Transmission Nematic
- STN Super Twisted Nematic
- IPS In-Planes Switching
- VA Very Alignment
- OCB Optic Optical
- An appropriate liquid crystal mode such as a birefringence type can be applied.
- the organic EL display element having the color filter of the present invention can adopt an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.
- the electronic paper provided with the color filter of the present invention can adopt an appropriate structure, and examples thereof include a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.
- the pigment dispersion (A-1) was prepared by processing with a bead mill.
- Dye solution preparation example 1 A dye solution A was prepared by mixing 5 parts by mass of the compound A represented by the following formula and 95 parts by mass of propylene glycol monomethyl ether as a solvent.
- Dye solution preparation example 2 A dye solution B was prepared by mixing 5 parts by mass of Compound B represented by the following formula and 95 parts by mass of propylene glycol monomethyl ether as a solvent.
- Dye solution preparation example 3 A dye solution C was prepared by mixing 5 parts by mass of the compound C represented by the following formula and 95 parts by mass of propylene glycol monomethyl ether as a solvent.
- Dye solution preparation example 4 The dye solution D was prepared by mixing 5 parts by mass of the compound D represented by the following formula and 95 parts by mass of propylene glycol monomethyl ether as a solvent.
- Dye solution preparation example 5 A dye solution E was prepared by mixing 5 parts by mass of the compound E represented by the following formula and 95 parts by mass of propylene glycol monomethyl ether as a solvent.
- Synthesis example 1 A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heated to 80 ° C., at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate 23 parts by mass, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) The solution was added dropwise over a period of time and polymerized for 2 hours while maintaining this temperature.
- binder resin (b) This binder resin is referred to as “binder resin (b)”.
- Example 1 13.6 parts by mass of pigment dispersion (A-1), 27.2 parts by mass of dye solution A, 21.6 parts by mass of binder resin (b) as binder resin, M manufactured by Toagosei Co., Ltd.
- component (C) -402 mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate
- 9.2 parts by mass 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- as a photopolymerization initiator Tetraphenyl-1,2'-biimidazole (1.7 parts by mass), hydrogen donor 4,4'-bis (diethylamino) benzophenone (0.3 parts by mass) and 2-mercaptobenzothiazole (0.2 parts by mass), fluorine-based interface Mix 0.2 parts by mass of MegaFac F-554 manufactured by DIC Corporation as an activator and 3-methoxybutyl acetate as a solvent to obtain a solid content of 20 The amount% of the coloring composition was prepared.
- the obtained colored composition was applied on a glass substrate using a spin coater and then pre-baked for 10 minutes on a hot plate at 80 ° C. to form a coating film having a thickness of about 2.5 ⁇ m.
- the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was applied to each coating film at a dose of 2,000 J / m 2 without using a photomask. Exposed. In this manner, two evaluation substrates having a blue evaluation cured film formed on the substrate were produced.
- Example 2 a colored composition was prepared in the same manner as in Example 1 except that the types and amounts of the constituent components were changed as shown in Table 1. Then, the obtained colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
- each component is as follows.
- C-1 M-402 manufactured by Toagosei Co., Ltd. (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)
- D-1 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole
- D-2 Ethanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)
- D-3 4,4′-bis (diethylamino) benzophenone (hydrogen donor)
- D-4 2-mercaptobenzothiazole (hydrogen donor)
- D-5 Photopolymerization initiator represented by the following formula (13)
- E-1 Fluorosurfactant Megafac F-554 manufactured by DIC Corporation
- E-2 Commercially available phosphate surfactant (hydroxyethylene oxide phosphate ester)
- E-3 Commercially available sulfonic acid surfactant (polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate)
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Abstract
Description
したがって、本発明の課題は、耐熱性等と共に、耐溶剤性にも優れたカラーフィルタを製造することができる着色組成物を提供することにある。さらに、本発明の課題は、当該着色組成物を用いて形成された着色層を備えてなるカラーフィルタ、及び当該カラーフィルタを具備する表示素子を提供することにある。
(A)着色剤としてシアノ基、ハロゲン化炭化水素基及びハロスルホニル基よりなる群から選ばれる少なくとも1種の電子吸引基を有するアニオンを有する塩基性着色剤(以下、「特定着色剤」とも称する。)を含有し、
(D)光重合開始剤として分子間水素引き抜き型の光ラジカル開始剤を含有することを特徴とする着色組成物を提供するものである。
本発明においては、分子間水素引き抜き型の光ラジカル開始剤として、ビイミダゾール系化合物を含有することが好ましい。
したがって、本発明の着色組成物は、カラー液晶表示素子用カラーフィルタ、固体撮像素子の色分解用カラーフィルタ、有機EL表示素子用カラーフィルタ、電子ペーパー用カラーフィルタを始めとする各種のカラーフィルタの作製に極めて好適に使用することができる。
着色組成物
以下、本発明の着色組成物の構成成分について説明する。
-(A)着色剤-
本発明の着色組成物は、着色剤として、特定着色剤、即ちシアノ基、ハロゲン化炭化水素基及びハロスルホニル基よりなる群から選ばれる少なくとも1種の電子吸引基を有するアニオンを有する塩基性着色剤を含有することを特徴とする。塩基性着色剤とは、カチオン部が発色団となるイオン性着色剤であり、好ましくは塩基性染料である。
本発明の着色組成物において、特定着色剤は、単独で又は2種以上を混合して使用することができる。
特定着色剤におけるアニオン部は、シアノ基、ハロゲン化炭化水素基及びハロスルホニル基よりなる群から選ばれる少なくとも1種の電子吸引基を有するアニオンであれば特に限定されるものではないが、例えば、下記式(1a)~(1e)で表されるアニオンを挙げることができる。
R20はアルキル基、脂環式炭化水素基、ヘテロアリール基又は置換若しくは非置換のアリール基を示すが、アルキル基は直鎖状でも分岐鎖状でもよく、アルキル基の炭素数は1~12、更に1~8が好ましい。脂環式炭化水素基は2~4環の橋かけ脂環式炭化水素基でもよく、脂環式炭化水素基の炭素数は3~20、更に3~12が好ましい。ヘテロアリール基としては、窒素原子、酸素原子及び硫黄原子から選ばれる1以上のヘテロ原子を含む5~10員の芳香族複素環から構成される基が好ましい。アリール基としては、炭素数6~14、更に6~10のアリール基が好ましく、特にフェニル基が好ましい。なお、置換基としては、例えば、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、ハロ基又はトリフルオロメチル基が挙げられ、置換基の位置及び数は任意であり、置換基を2以上有する場合、当該置換基は同一でも異なっていてもよい。
また、R21はアルカンジイル基を示すが、その炭素数は1~12、更に1~6が好ましい。具体的には、メチレン基、エチレン基、エタン-1,1-ジイル基、プロパン-1,1-ジイル基、プロパン-1,2-ジイル基、プロパン-1,3-ジイル基、プロパン-2,2-ジイル基、ブタン-1,2-ジイル基、ブタン-1,3-ジイル基、ブタン-1,4-ジイル基、ペンタン-1,4-ジイル基、ペンタン-1,5-ジイル基、ヘキサン-1,5-ジイル基、ヘキサン-1,6-ジイル基等を挙げることができる。中でも、製造し易さの点から、エチレン基が好ましい。
なお、nの上限は、10が好ましく、8がより好ましい。
また、式(1-2)においては、R22~R26のうち少なくとも3つがフッ素原子又はフッ化アルキル基であることが好ましい。
ハロゲン化アルキルスルホニル基としては、パーフルオロアルキルスルホニル基が好ましく、例えば、CF3SO2基、CF3CF2SO2基、(CF3)2CFSO2基、CF3CF2CF2SO2基、CF3CF2CF2CF2SO2基、(CF3)2CFCF2SO2基、CF3CF2(CF3)CFSO2基、(CF3)3CSO2基が挙げられる。中でも、CF3SO2基が好ましい。
式(1a-2)において、R1bは連結基を有していてもよいハロゲン化アルカンジイル基を示す。〕
R6及びR7は、相互に独立に、水素原子、炭素数1~8の鎖状若しくは環状のアルキル基、フェニル基又はエチレン性不飽和結合を有する基を示し、
R8及びR9は、相互に独立に、水素原子、炭素数1~8の鎖状若しくは環状のアルキル基、フェニル基又はエチレン性不飽和結合を有する基を示し、
R10は、水素原子、塩素原子、炭素数1~8の鎖状若しくは環状のアルキル基又は-COOR17(R17は水素原子又は炭素数1~8の鎖状若しくは環状のアルキル基を示す。)を示し、
R11及び14は、相互に独立に、水素原子、炭素数1~8の鎖状若しくは環状のアルキル基を示すか、又はR11とR14とが一緒になって硫黄原子を示し、
R12及びR13は、相互に独立に、水素原子、塩素原子又は炭素数1~8の鎖状若しくは環状のアルキル基を示し、
Yは、水素原子又は下記式(3);
R15及びR16は、相互に独立に、水素原子、炭素数1~8の鎖状若しくは環状のアルキル基、フェニル基又はエチレン性不飽和結合を有する基を示す。〕
R6~R14(-COOR17におけるR17を含む)、R15及びR16における炭素数1~8の鎖状若しくは環状のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、第二ブチル基、第三ブチル基、イソブチル基、シクロブチル基、アミル基、第三アミル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、シクロヘプチル基、オクチル基、イソオクチル基、第三オクチル基、2-エチルヘキシル基などを挙げることができる。
R6~R9、R15及びR16におけるエチレン性不飽和結合を有する基としては、特に限定されるものではないが、例えば、CH2=CH-COO-R18-、CH2=C(CH3)-COO-R18-、CH2=CH-Ph-R18-、CH2=C(CH3)-Ph-R18-及びCH2=CH-CO-(R18は、炭素数1~4のアルカンジイル基を示し、Phはフェニレン基を示す。)などを挙げることができる。
R18における炭素数1~4のアルカンジイル基としては、例えば、メチレン基、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基などを挙げることができる。
他の着色剤としては、用途に応じて色彩や材質を適宜選択することができる。具体的には、顔料、染料及び天然色素の何れをも使用することができるが、カラーフィルタを構成する着色層には高い色純度、輝度、コントラスト、遮光性等が求められることから、顔料及び染料から選ばれる少なくとも1種を使用することが好ましい。
C.I.ソルベントレッド45、C.I.ソルベントレッド49;
C.I.ソルベントオレンジ2、C.I.ソルベントオレンジ7、C.I.ソルベントオレンジ11、C.I.ソルベントオレンジ15、C.I.ソルベントオレンジ26、C.I.ソルベントオレンジ56;
C.I.ソルベントブルー35、C.I.ソルベントブルー37、C.I.ソルベントブルー59、C.I.ソルベントブルー67;
C.I.アシッドレッド91、C.I.アシッドレッド92、C.I.アシッドレッド97、C.I.アシッドレッド114、C.I.アシッドレッド138、C.I.アシッドレッド151;
C.I.アシッドオレンジ51、C.I.アシッドオレンジ63;
C.I.アシッドブルー80、C.I.アシッドブルー83、C.I.アシッドブルー90;
C.I.アシッドグリーン9、C.I.アシッドグリーン16、C.I.アシッドグリーン25、C.I.アシッドグリーン27。
また本発明において、特定着色剤と他の着色剤とを併用する場合、特定着色剤の含有割合は、全着色剤中、5~80質量%、更に15~70質量%、更に30~60質量%であることが好ましい。中でも、特定着色剤としてのトリアリールメタン系着色剤と他の着色剤とを併用する場合、トリアリールメタン系着色剤の含有割合は、全着色剤中、20~80質量%、更に20~60質量%、更に30~50質量%であることが好ましい。
また、上記分散助剤としては、例えば、顔料誘導体を挙げることができ、具体的には、銅フタロシアニン、ジケトピロロピロール、キノフタロンのスルホン酸誘導体等を挙げることができる。なお、分散剤及び分散助剤の含有量は、本発明の目的を阻害しない範囲内で適宜決定することが可能である。
本発明におけるバインダー樹脂としては、特に限定されるものではないが、カルボキシル基、フェノール性水酸基等の酸性官能基を有する樹脂であることが好ましい。中でも、カルボキシル基を有する重合体(以下、「カルボキシル基含有重合体」という。)が好ましく、例えば、1個以上のカルボキシル基を有するエチレン性不飽和単量体(以下、「不飽和単量体(b1)」という。)と他の共重合可能なエチレン性不飽和単量体(以下、「不飽和単量体(b2)」という。)との共重合体を挙げることができる。
これらの不飽和単量体(b1)は、単独で又は2種以上を混合して使用することができる。
N-フェニルマレイミド、N-シクロヘキシルマレイミドの如きN-位置換マレイミド;
スチレン、α-メチルスチレン、p-ヒドロキシスチレン、p-ヒドロキシ-α-メチルスチレン、p-ビニルベンジルグリシジルエーテル、アセナフチレンの如き芳香族ビニル化合物;
ポリスチレン、ポリメチル(メタ)アクリレート、ポリ-n-ブチル(メタ)アクリレート、ポリシロキサンの如き重合体分子鎖の末端にモノ(メタ)アクリロイル基を有するマクロモノマー等を挙げることができる。
これらの不飽和単量体(b2)は、単独で又は2種以上を混合して使用することができる。
本発明において(C)2個以上のエチレン性不飽和基を有する化合物としては、特に限定されるものではないが、2個以上の(メタ)アクリロイル基を有する化合物が好ましい。
本発明において、(C)2個以上のエチレン性不飽和基を有する化合物は、単独で又は2種以上を混合して使用することができる。
(D)光重合開始剤は、可視光線、紫外線、遠紫外線、電子線、X線等の放射線の露光により、上記(C)2個以上のエチレン性不飽和基を有する化合物の重合反応を開始しうる活性種を発生する化合物である。本発明の着色組成物は、(D)光重合開始剤として、分子間水素引き抜き型の光ラジカル開始剤を含有することを特徴とする。これにより、耐溶剤性に優れた着色層を形成することができる着色組成物が得られる。
2,2'-ビス(2-クロロフェニル)-4,4',5,5'-テトラキス(4-エトキシカルボニルフェニル)-1,2'-ビイミダゾール、2,2'-ビス(2-ブロモフェニル)-4,4',5,5'-テトラキス(4-エトキシカルボニルフェニル)-1,2'-ビイミダゾール等のビス(ハロゲン置換フェニル)テトラキス(アルコキシカルボニルフェニル)ビイミダゾール;
2,2'-ビス(2-クロロフェニル)-4,4',5,5'-テトラフェニル-1,2'-ビイミダゾール、2,2'-ビス(2,4-ジクロロフェニル)-4,4',5,5'-テトラフェニル-1,2'-ビイミダゾール、2,2'-ビス(2,4,6-トリクロロフェニル)-4,4',5,5'-テトラフェニル-1,2'-ビイミダゾール、2,2'-ビス(2-ブロモフェニル)-4,4',5,5'-テトラフェニル-1,2'-ビイミダゾール、2,2'-ビス(2,4-ジブロモフェニル)-4,4',5,5'-テトラフェニル-1,2'-ビイミダゾール、2,2'-ビス(2,4,6-トリブロモフェニル)-4,4',5,5'-テトラフェニル-1,2'-ビイミダゾール等のビス(ハロゲン置換フェニル)テトラフェニルビイミダゾール
を挙げることができる。
ビイミダゾール系化合物は、単独で又は2種以上を混合して使用することができる。
メルカプタン系水素供与体は、ベンゼン環あるいは複素環をそれぞれ1個以上有することも、またベンゼン環と複素環との両者を有することもできる。これらの環を2個以上有する場合、縮合環を形成していてもよい。
また、メルカプタン系水素供与体は、メルカプト基を2個以上有する場合、少なくとも1個の遊離メルカプト基が残存する限りでは、残りのメルカプト基の1個以上がアルキル基、アラルキル基又はアリール基で置換されていてもよい。更には、少なくとも1個の遊離メルカプト基が残存する限りでは、2個の硫黄原子がアルキレン基等の2価の有機基を介在して結合した構造単位、あるいは2個の硫黄原子がジスルフィドの形で結合した構造単位を有することができる。
更に、メルカプタン系水素供与体は、メルカプト基以外の箇所で、カルボキシル基、アルコキシカルボニル基、置換アルコキシカルボニル基、フェノキシカルボニル基、置換フェノキシカルボニル基、ニトリル基等によって置換されていてもよい。
これらのメルカプタン系水素供与体のうち、2-メルカプトベンゾチアゾール等のメルカプト置換ベンゾチアゾール、2-メルカプトベンゾオキサゾール等のメルカプト置換ベンゾオキサゾールが好ましく、更にメルカプト置換ベンゾチアゾールが好ましく、特に2-メルカプトベンゾチアゾールが好ましい。
また、アミン系水素供与体は、全てのアミノ基が第一級アミノ基であってもよく、アミノ基の1個以上が、アルキル基若しくは置換アルキル基で置換された第二級アミノ基又は第三級アミノ基であってもよく、またアミノ基以外の箇所で、カルボキシル基、アルコキシカルボニル基、置換アルコキシカルボニル基、フェノキシカルボニル基、置換フェノキシカルボニル基、ニトリル基等によって置換されていてもよい。
これらのアミン系水素供与体のうち、4,4'-ビス(ジメチルアミノ)ベンゾフェノン、4,4'-ビス(ジエチルアミノ)ベンゾフェノン等のアミノ置換ベンゾフェノンが好ましく、特に4,4'-ビス(ジエチルアミノ)ベンゾフェノンが好ましい。
なお、アミン系水素供与体は、ビイミダゾール系化合物以外の光重合開始剤の場合においても、増感剤としての作用を有するものである。
本発明において、水素供与体は、単独で又は2種以上を混合して使用することができる。
また、ビイミダゾール系化合物100質量部に対する水素供与体の含有量は、5~60質量部、更に10~40質量部であることが好ましい。
分子間水素引き抜き型の光ラジカル開始剤の含有割合は、所望の効果を高める点から、全光重合開始剤中、好ましくは50質量%以上、より好ましくは60質量%以上、更に好ましくは70質量%以上である。なお、上限は特に限定されないが、90質量%、80質量%が好ましい。
着色剤として塩基性染料又は塩基性レーキ顔料を使用する場合、(E)アニオン性界面活性剤を含有せしめることにより、それらの耐熱性を高めることができる。アニオン性界面活性剤としては、特に限定されるものではなく、例えば、カルボン酸系界面活性剤、リン酸系界面活性剤、スルホン酸系界面活性剤等を挙げることができる。
また、上記リン酸系界面活性剤の具体例としては、ヒドロキシエチレンオキシドリン酸エステル、ヒドロキシエチレンオキシドリン酸エステルのナトリウム塩、エチレンオキサイドアルキルリン酸エステル、ポリオキシエチレンスチレン化フェニルエーテルリン酸エステル等を挙げることができる。
また、上記スルホン酸系界面活性剤の具体例としては、ドデシルベンゼンスルホン酸ナトリウム、ラウリル硫酸トリエタノールアミン塩、ラウリル硫酸アンモニウム、ラウリル硫酸ナトリウム、ジアルキルスルホコハク酸ナトリウム、アルキルナフタレンスルホン酸ナトリウム、アルキルジフェニルエーテルジスルホン酸ナトリウム、ポリオキシエチレンスチレン化フェニルエーテル硫酸アンモニウム、ポリオキシエチレンラウリルエーテル硫酸アンモニウム、ポリオキシエチレン-1-(アリルオキシメチル)アルキルエーテル硫酸アンモニウム、ポリオキシエチレンノニルプロペニルフェニルエーテル硫酸アンモニウム等を挙げることができる。
本発明の着色組成物には、上記(C)2個以上のエチレン性不飽和基を有する化合物以外の架橋剤(以下、単に「(F)架橋剤」とも称する)を含有せしめることにより、更に耐熱性や耐溶剤性を高めることができる。このような(F)架橋剤としては、例えば、2個以上のエポキシ基を有する化合物、N-メチロール基及びN-アルコキシメチル基から選ばれる基を合計2個以上有する化合物等を挙げることができる。
本発明において、(F)架橋剤は、単独で又は2種以上を混合して使用することができる。
本発明の着色組成物は、上記(A)~(D)成分、及び任意的に加えられる他の成分を含有するものであるが、通常、溶媒を配合して液状組成物として調製される。
上記溶媒としては、着色組成物を構成する(A)~(D)成分や他の成分を分散又は溶解し、かつこれらの成分と反応せず、適度の揮発性を有するものである限り、適宜に選択して使用することができる。
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノ-n-プロピルエーテル、エチレングリコールモノ-n-ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ-n-プロピルエーテル、ジエチレングリコールモノ-n-ブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ-n-プロピルエーテル、プロピレングリコールモノ-n-ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノ-n-プロピルエーテル、ジプロピレングリコールモノ-n-ブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノエチルエーテル等の(ポリ)アルキレングリコールモノアルキルエーテル類;
メタノール、エタノール、プロパノール、ブタノール、イソプロパノール、イソブタノール、t-ブタノール、オクタノール、2-エチルヘキサノール、シクロヘキサノール等の(シクロ)アルキルアルコール類;
ジアセトンアルコール等のケトアルコール類;
ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジエチルエーテル、テトラヒドロフラン等の他のエーテル類;
メチルエチルケトン、シクロヘキサノン、2-ヘプタノン、3-ヘプタノン等のケトン類;
3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エトキシ酢酸エチル、3-メチル-3-メトキシブチルプロピオネート等のアルコキシカルボン酸エステル類;
酢酸エチル、酢酸n-プロピル、酢酸i-プロピル、酢酸n-ブチル、酢酸i-ブチル、ぎ酸n-アミル、酢酸i-アミル、プロピオン酸n-ブチル、酪酸エチル、酪酸n-プロピル、酪酸i-プロピル、酪酸n-ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸n-プロピル、アセト酢酸メチル、アセト酢酸エチル、2-オキソブタン酸エチル等の他のエステル類;
トルエン、キシレン等の芳香族炭化水素類;
N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン等のアミド又はラクタム類
等を挙げることができる。
本発明において、溶媒は、単独で又は2種以上を混合して使用することができる。
本発明の着色組成物は、必要に応じて、種々の添加剤を含有することもできる。
添加剤としては、例えば、ガラス、アルミナ等の充填剤;ポリビニルアルコール、ポリ(フロオロアルキルアクリレート)類等の高分子化合物;フッ素系界面活性剤、シリコン系界面活性剤等の界面活性剤;ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(2-メトキシエトキシ)シラン、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-クロロプロピルメチルジメトキシシラン、3-クロロプロピルトリメトキシシラン、3-メタクリロイロキシプロピルトリメトキシシラン、3-メルカプトプロピルトリメトキシシラン等の密着促進剤;2,2-チオビス(4-メチル-6-t-ブチルフェノール)、2,6-ジ-t-ブチルフェノール等の酸化防止剤;2-(3-t-ブチル-5-メチル-2-ヒドロキシフェニル)-5-クロロベンゾトリアゾール、アルコキシベンゾフェノン類等の紫外線吸収剤;ポリアクリル酸ナトリウム等の凝集防止剤;マロン酸、アジピン酸、イタコン酸、シトラコン酸、フマル酸、メサコン酸、2-アミノエタノール、3-アミノ-1-プロパノール、5-アミノ-1-ペンタノール、3-アミノ-1,2-プロパンジオール、2-アミノ-1,3-プロパンジオール、4-アミノ-1,2-ブタンジオール等の残渣改善剤;こはく酸モノ〔2-(メタ)アクリロイロキシエチル〕、フタル酸モノ〔2-(メタ)アクリロイロキシエチル〕、ω-カルボキシポリカプロラクトンモノ(メタ)アクリレート等の現像性改善剤;特開2008-242078号公報等に開示されている反応性官能基を有するシロキサンオリゴマー等を挙げることができる。
本発明のカラーフィルタは、本発明の着色組成物を用いて形成された着色層を備えてなるものである。
また、これらの基板には、所望により、シランカップリング剤等による薬品処理、プラズマ処理、イオンプレーティング、スパッタリング、気相反応法、真空蒸着等の適宜の前処理を施しておくこともできる。
また、上記アルカリ現像液としては、例えば、炭酸ナトリウム、水酸化ナトリウム、水酸化カリウム、テトラメチルアンモニウムハイドロオキサイド、コリン、1,8-ジアザビシクロ-[5.4.0]-7-ウンデセン、1,5-ジアザビシクロ-[4.3.0]-5-ノネン等の水溶液が好ましい。
現像処理法としては、シャワー現像法、スプレー現像法、ディップ(浸漬)現像法、パドル(液盛り)現像法等を適用することができる。現像条件は、常温で5~300秒が好ましい。
このようにして形成された画素の膜厚は、通常0.5~5μm、好ましくは1~3μmである。
カラーフィルタを形成する際に使用される基板や放射線の光源、また、プレベークやポストベークの方法や条件は、上記した第一の方法と同様である。このようにして、インクジェット方式により形成された画素の膜厚は、隔壁の高さと同程度である。
このようにして得られる本発明のカラーフィルタは、輝度及び色純度が極めて高いため、カラー液晶表示素子、カラー撮像管素子、カラーセンサー、有機EL表示素子、電子ペーパー等に極めて有用である。
本発明の表示素子は、本発明のカラーフィルタを具備するものである。表示素子としては、カラー液晶表示素子、有機EL表示素子、電子ペーパー等を挙げることができる。
本発明のカラーフィルタを具備するカラー液晶表示素子は、透過型でも反射型でもよく、適宜の構造をとることができる。例えば、カラーフィルタを、薄膜トランジスター(TFT)が配置された駆動用基板とは別の基板上に形成して、駆動用基板とカラーフィルタを形成した基板とが、液晶層を介して対向した構造をとることができ、さらに薄膜トランジスター(TFT)が配置された駆動用基板の表面上にカラーフィルタを形成した基板と、ITO(錫をドープした酸化インジュウム)電極あるいはIZO(酸化インジュウムと酸化亜鉛との混合物)電極を形成した基板とが、液晶層を介して対向した構造をとることもできる。後者の構造は、開口率を格段に向上させることができ、明るく高精細な液晶表示素子が得られるという利点を有する。
顔料分散液調製例1
着色剤としてC.I.ピグメントブルー15:6を15質量部、分散剤としてBYK-LPN21116(ビックケミー(BYK)社製)12.5質量部(固形分濃度=40質量%)、溶媒としてプロピレングリコールモノメチルエーテルアセテート72.5質量部を用いて、ビーズミルにより処理して、顔料分散液(A-1)を調製した。
染料溶液調製例1
下記式で表される化合物Aを5質量部、溶媒としてプロピレングリコールモノメチルエーテル95質量部を混合し、染料溶液Aを調製した。
下記式で表される化合物Bを5質量部、溶媒としてプロピレングリコールモノメチルエーテル95質量部を混合し、染料溶液Bを調製した。
下記式で表される化合物Cを5質量部、溶媒としてプロピレングリコールモノメチルエーテル95質量部を混合し、染料溶液Cを調製した。
下記式で表される化合物Dを5質量部、溶媒としてプロピレングリコールモノメチルエーテル95質量部を混合し、染料溶液Dを調製した。
下記式で表される化合物Eを5質量部、溶媒としてプロピレングリコールモノメチルエーテル95質量部を混合し、染料溶液Eを調製した。
合成例1
冷却管と攪拌機を備えたフラスコに、プロピレングリコールモノメチルエーテルアセテート100質量部を仕込んで窒素置換した。80℃に加熱して、同温度で、プロピレングリコールモノメチルエーテルアセテート100質量部、メタクリル酸20質量部、スチレン10質量部、ベンジルメタクリレート5質量部、2-ヒドロキシエチルメタクリレート15質量部、2-エチルヘキシルメタクリレート23質量部、N-フェニルマレイミド12質量部、こはく酸モノ(2-アクリロイロキシエチル)15質量部及び2,2’-アゾビス(2,4-ジメチルバレロニトリル)6質量部の混合溶液を1時間かけて滴下し、この温度を保持して2時間重合した。その後、反応溶液の温度を100℃に昇温させ、さらに1時間重合することにより、バインダー樹脂溶液(固形分濃度=33質量%)を得た。
得られたバインダー樹脂は、Mw=12,200、Mn=6,500であった。このバインダー樹脂を「バインダー樹脂(b)」とする。
実施例1
顔料分散液(A-1)13.6質量部、染料溶液Aを27.2質量部、バインダー樹脂としてバインダー樹脂(b)溶液21.6質量部、(C)成分として東亞合成株式会社製M-402(ジペンタエリスリトールヘキサアクリレートとジペンタエリスリトールペンタアクリレートの混合物)9.2質量部、光重合開始剤として2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾール1.7質量部、水素供与体として4,4’-ビス(ジエチルアミノ)ベンゾフェノン0.3質量部と2-メルカプトベンゾチアゾール0.2質量部、フッ素系界面活性剤としてDIC株式会社製メガファックF-554を0.2質量部、及び溶媒として3-メトキシブチルアセテートを混合して、固形分濃度20質量%の着色組成物を調製した。
次いで、この基板を室温に冷却したのち、高圧水銀ランプを用い、フォトマスクを介さずに、各塗膜に365nm、405nm及び436nmの各波長を含む放射線を2,000J/m2の露光量で露光した。このようにして、基板上に青色の評価用硬化膜を形成した評価用基板2枚を作製した。
評価用基板2枚のうち1枚を、230℃のクリーンオーブン内で1時間ポストベークした。ポストベーク前後の基板について、色差(ΔEab*)をカラーアナライザー(大塚電子(株)製MCPD2000)により測定した。そして、ΔEab*が3.0未満の場合を「◎」、3.0以上5.0未満の場合を「○」、5.0以上の場合を「×」として評価した。なお、ΔEab*値が低い程、良好であることを意味する。評価結果を表2に示す。
上記で得られた評価用基板2枚のうちの残る1枚を、25℃のプロピレングリコールモノメチルアセテートに30分間浸漬させた。この処理前後の膜厚を触針式膜厚測定機(アルファステップ社IQ、KLAテンコール社)で測定し、残膜率(処理後膜厚/処理前膜厚×100)を算出した。そして、残膜率が90%以上の場合を「◎」、80%以上90%未満の場合を「○」、80%未満の場合を「×」として評価した。なお、残膜率が高い程、良好であることを意味する。評価結果を表2に示す。
実施例1において、構成成分の種類及び量を表1に示すように変更した以外は実施例1と同様に着色組成物を調製した。そして、得られた着色組成物について実施例1と同様にして評価を行った。評価結果を表2に示す。
C-1:東亞合成株式会社製M-402(ジペンタエリスリトールヘキサアクリレートとジペンタエリスリトールペンタアクリレートの混合物)
D-1:2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾール
D-2:エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム)
D-3:4,4’-ビス(ジエチルアミノ)ベンゾフェノン(水素供与体)
D-4:2-メルカプトベンゾチアゾール(水素供与体)
D-5:下記式(13)で表される光重合開始剤
E-2:市販のリン酸系界面活性剤(ヒドロキシエチレンオキシドリン酸エステル)
E-3:市販のスルホン酸系界面活性剤(ポリオキシエチレン-1-(アリルオキシメチル)アルキルエーテル硫酸アンモニウム)
Claims (8)
- (A)着色剤、(B)バインダー樹脂、(C)2個以上のエチレン性不飽和基を有する化合物並びに(D)光重合開始剤を含有する着色組成物であって、
(A)着色剤としてシアノ基、ハロゲン化炭化水素基及びハロスルホニル基よりなる群から選ばれる少なくとも1種の電子吸引基を有するアニオンを有する塩基性着色剤を含有し、
(D)光重合開始剤として分子間水素引き抜き型の光ラジカル開始剤を含有することを特徴とする着色組成物。 - (A)着色剤、(B)バインダー樹脂、(C)2個以上のエチレン性不飽和基を有する化合物並びに(D)光重合開始剤を含有する着色組成物であって、
(A)着色剤としてシアノ基、ハロゲン化炭化水素基及びハロスルホニル基よりなる群から選ばれる少なくとも1種の電子吸引基を有するアニオンを有する塩基性着色剤を含有し、
(D)光重合開始剤としてビイミダゾール系化合物を含有することを特徴とする着色組成物。 - 電子吸引基を有する前記アニオンが下記式(1a)~(1e)のいずれかで表されるアニオンである、請求項1又は2に記載の着色組成物。
- 前記塩基性着色剤がトリアリールメタン系着色剤である、請求項1~3のいずれか1項に記載の着色組成物。
- 前記分子間水素引き抜き型の光ラジカル開始剤の含有割合が全光重合開始剤中50質量%以上である、請求項1、3及び4のいずれか1項に記載の着色組成物。
- 前記ビイミダゾール系化合物の含有割合が全光重合開始剤中50質量%以上である、請求項2~4のいずれか1項に記載の着色組成物。
- 請求項1~6のいずれか1項に記載の着色組成物を用いて形成された着色層を備えてなるカラーフィルタ。
- 請求項7に記載のカラーフィルタを具備する表示素子。
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