WO2014196396A1 - 着色組成物、着色硬化膜及び表示素子 - Google Patents
着色組成物、着色硬化膜及び表示素子 Download PDFInfo
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- WO2014196396A1 WO2014196396A1 PCT/JP2014/063818 JP2014063818W WO2014196396A1 WO 2014196396 A1 WO2014196396 A1 WO 2014196396A1 JP 2014063818 W JP2014063818 W JP 2014063818W WO 2014196396 A1 WO2014196396 A1 WO 2014196396A1
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- C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
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- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
- C09B29/0029—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom
- C09B29/0037—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom containing a five-membered heterocyclic ring with two nitrogen atoms
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- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
- C09B29/0029—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom
- C09B29/004—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom containing a five-membered heterocyclic ring with three nitrogen atoms
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- C09B29/0029—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom
- C09B29/0048—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom containing a six-membered heterocyclic ring with one nitrogen atom
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- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
- C09B29/0074—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms
- C09B29/0077—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms containing a five-membered heterocyclic ring with one nitrogen and one sulfur as heteroatoms
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- C09B29/0805—Amino benzenes free of acid groups
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- C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
- C09B29/081—Amino benzenes free of acid groups characterised by the amino group substituted amino group unsubstituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino, aralkylamino or arylamino
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- C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
- C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
- C09B29/0823—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by CN
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- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3608—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered heterocyclic ring with only one nitrogen as heteroatom
- C09B29/3613—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered heterocyclic ring with only one nitrogen as heteroatom from an indole
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- C09B44/108—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system characterised by a cyclammonium six-membered specific ring not mentioned hereafter, e.g. pyrimidinium, perimidinium, pyridazonium, oxazinium
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- C09B57/08—Naphthalimide dyes; Phthalimide dyes
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- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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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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- 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
Definitions
- the present invention relates to a colored composition, a colored cured film, and a display element, and more specifically, a colored cured film used for a transmissive or reflective color liquid crystal display element, solid-state imaging element, organic EL display element, electronic paper, and the like.
- the present invention relates to a colored composition used for forming a colored cured film, a colored cured film formed using the colored composition, and a display element including the colored cured film.
- 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 of obtaining pixels of each color by irradiation (hereinafter referred to as “exposure”) and development is known (see, for example, Patent Documents 1 and 2).
- a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed see, for example, Patent Document 3
- a method for obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (for example, see Patent Document 4).
- Patent Document 5 proposes the use of a triarylmethane dye having an alkylsulfonylimide anion as a dye-containing coloring composition capable of forming a pixel having excellent heat resistance.
- the subject of this invention is providing the coloring composition suitable for formation of the colored cured film which can make heat resistance and solvent resistance compatible. Furthermore, the subject of this invention is providing the colored cured film formed using the said coloring composition, and the display element which comprises the same.
- the present invention is a coloring composition
- a coloring composition comprising (A) a colorant and (B) a polymerizable compound, wherein the colorant has a structural unit represented by the following formula (1) (hereinafter, “ The present invention also provides a coloring composition containing the present coloring agent.
- R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group
- R 2 and R 3 each independently represent a hydrogen atom, a halo group, or a substituted or unsubstituted hydrocarbon.
- at least one of R 2 and R 3 is a halo group or a halo group-substituted hydrocarbon group.
- A represents a divalent group
- G represents a divalent hydrocarbon group or a single bond.
- the divalent hydrocarbon group may have a linking group selected from —O— group, —S— group, —CO— group, and —NR 7 — group between CC bonds.
- R 7 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
- Z m + represents a cationic chromophore, m represents a natural number of 1 to 3, p represents a natural number of 1 to 8. ]
- the present invention also provides a colored cured film formed using the colored composition, and a display element comprising the colored cured film.
- the “colored cured film” means each color pixel, black matrix, black spacer, and the like used for a display element and a solid-state imaging element.
- the colored composition of the present invention can be used very suitably for the production of solid-state imaging devices such as color liquid crystal display devices, organic EL display devices, display devices such as electronic paper, and CMOS image sensors.
- Coloring composition Hereinafter, the structural component of the coloring composition of this invention is demonstrated in detail.
- the coloring composition of this invention contains this coloring agent as a coloring agent.
- the present colorant is a compound having a structural unit represented by the following formula (1), and in the compound, an anion having an SO 3 ⁇ group at the terminal and a cation forming the chromophore form a salt. Is.
- R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group
- R 2 and R 3 each independently represent a hydrogen atom, a halo group, or a substituted or unsubstituted hydrocarbon group.
- at least one of R 2 and R 3 is a halo group or a halo group-substituted hydrocarbon group.
- A represents a divalent group
- G represents a divalent hydrocarbon group or a single bond.
- the divalent hydrocarbon group may have a linking group selected from —O— group, —S— group, —CO— group, and —NR 7 — group between CC bonds.
- R 7 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
- Z m + represents a cationic chromophore, m independently represents a natural number of 1 to 3, p represents a natural number of 1 to 8.
- R 1 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
- halo group for R 2 and R 3 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a fluorine atom is preferable.
- the hydrocarbon group according to R 2 , R 3 and R 7 may be linear, branched or cyclic, and may have a bridged structure. Specific examples include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. In addition, the hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may have an unsaturated bond either in the molecule or at the end.
- the aliphatic hydrocarbon group is preferably an alkyl group, and the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 6 carbon atoms. Specific examples include methyl group, ethyl group, isopropyl group, propyl group, butyl group, 2-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like.
- the alicyclic hydrocarbon is preferably a cycloalkyl group, and the cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, still more preferably 3 to 6 carbon atoms. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.
- the aromatic hydrocarbon group is preferably an aryl group or an aralkyl group, the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and the aralkyl group preferably has 7 to 20 carbon atoms, preferably 7 to 16 is more preferable.
- the “aryl group” refers to a monocyclic to tricyclic aromatic hydrocarbon group, and examples thereof include a phenyl group, a naphthyl group, a biphenyl group, and an anthranyl group.
- the aralkyl group examples include benzyl group, phenethyl group, ⁇ -methylbenzyl group, 2-phenylpropan-2-yl group and the like.
- the substituent that the hydrocarbon group has include a halo group, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms.
- the hydrocarbon group is an alicyclic hydrocarbon group or an aromatic hydrocarbon group
- the substituent As an alkyl group having 1 to 6 carbon atoms.
- the halo group and the alkyl group having 1 to 6 carbon atoms include those described above.
- alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group and the like.
- a substituent of a hydrocarbon group a halo group is preferable and a fluorine atom is still more preferable.
- R 2 and R 3 are preferably a halo group or a halo group-substituted hydrocarbon group, more preferably a fluorine atom or a fluorine atom-substituted alkyl group, and even more preferably a fluorine atom or a perfluoroalkyl group.
- the perfluoroalkyl group preferably has 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms.
- trifluoromethyl group pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, undecafluoropentyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group, nona Decafluorononyl, heneicosadecyl, (1-trifluoromethyl) tetrafluoroethyl, (1-trifluoromethyl) hexafluoropropyl, 1,1-bistrifluoromethyl-2,2,2-tri A fluoroethyl group can be exemplified.
- At least one of R 2 and R 3 is a halo group or a halo group-substituted hydrocarbon group, but both R 2 and R 3 are preferably halo groups, and both are fluorine atoms. Further preferred.
- R 7 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be substituted with a fluorine atom.
- the divalent group related to A is preferably a divalent group containing a hetero atom, for example, —O— group, — (CO) O— group, —O (CO) — group, —CO— group, — Mention may be made of CONH-groups or -SO 2 -groups. Of these, —O— group, — (CO) O— group, and —CONH— group are preferable.
- Examples of the divalent hydrocarbon group for G include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.
- the divalent aliphatic hydrocarbon group may be either linear or branched, and the divalent aliphatic hydrocarbon group and the divalent alicyclic hydrocarbon group may be saturated hydrocarbons or unsaturated hydrocarbons. It may be a group.
- Examples of the divalent aliphatic hydrocarbon group include an alkanediyl group and an alkenediyl group, and the carbon number thereof is preferably 1 to 20, more preferably 2 to 12, and further preferably 2 to 6.
- Specific examples include methylene group, ethane-1,1-diyl group, ethane-1,2-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, 2-methylpropane-1,2-diyl group, 2,2-dimethylpropane-1,3-diyl group Ethene-1,1-diyl group, ethene-1,2-diyl group, propene-1,2-diyl group, propene-1,3-diyl group,
- Examples of the divalent alicyclic hydrocarbon group include a cycloalkylene group and a cycloalkenylene group, and the carbon number thereof is preferably 3 to 20, and more preferably 3 to 12. Specific examples include cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclobutenylene group, cyclopentenylene group, cyclohexenylene group and other monocyclic hydrocarbon ring groups, 1,4-norbornylene group, 2, Examples thereof include a norbornylene group such as a 5-norbornylene group, a bridged cyclic hydrocarbon ring group such as a 1,5-adamantylene group, and a 2,6-adamantylene group.
- the divalent hydrocarbon group for G may have a linking group selected from —O— group, —S— group, —CO— group, and —NR 7 — group between C—C bonds.
- the bonding position of the linking group is arbitrary.
- m represents a natural number of 1 to 3, and is appropriately selected so as to be electrically neutral with the anion portion according to the type of the cationic chromophore described later.
- p represents a natural number of 1 to 8, preferably a natural number of 1 to 6, more preferably a natural number of 2 to 6.
- Z m + is a cationic chromophore.
- the cationic chromophore related to Z m + is not particularly limited as long as it is a cation capable of forming a basic colorant together with the above-mentioned anion moiety, but preferably has an absorption maximum in the visible light region. Those having an absorption maximum at ⁇ 830 nm are more preferable, and those having an absorption maximum at 380 nm to 780 nm are more preferable.
- cationic chromophores examples include triarylmethane chromophore, methine chromophore, azo chromophore, diarylmethane chromophore, quinoneimine chromophore, anthraquinone chromophore, phthalocyanine chromophore, xanthene. And chromophores.
- Ar represents a substituted or unsubstituted aromatic hydrocarbon group.
- R 11 to R 14 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group, or a group having an ethylenically unsaturated bond.
- R 15 to R 22 represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, —COOR ′ or a halo group.
- R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
- Y represents a hydrogen atom or a group represented by the following formula (4).
- R 23 and R 24 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group or an ethylenically unsaturated bond. The group which has. ]
- the aromatic hydrocarbon group relating to Ar preferably has 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms. Specific examples include a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group.
- an alkyl group having 1 to 6 carbon atoms is preferable, and specific examples thereof include those described above.
- the aromatic hydrocarbon group related to Ar is preferably a phenylene group, a naphthylene group, a phenylene group substituted with an alkyl group having 1 to 6 carbon atoms, or a naphthylene group substituted with an alkyl group having 1 to 6 carbon atoms. .
- the alkyl group having 1 to 8 carbon atoms in R 11 to R 24 may be linear or branched, and specific examples thereof are the same as those described above. Can be mentioned. Among them, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable. Specific examples of the cycloalkyl group having 3 to 8 carbon atoms related to R 11 to R 14 include the same ones as described above.
- a cycloalkyl group having 3 to 6 carbon atoms is preferable, and a cyclohexyl group is particularly preferable.
- the group having an ethylenically unsaturated bond according to R 11 to R 14 include a vinyl group, a propenyl group, a styryl group, a (meth) acryloyloxyethyl group, a (meth) acryloyloxypropyl group, and a (meth) acryloylamide. Examples thereof include an ethyl group and a (meth) acryloylamidopropyl group.
- Specific examples of the halo group relating to R 15 to R 22 include the same ones as described above. Among these, a chlorine atom is preferable.
- the cations represented by the above formula (3) are particularly preferable from the viewpoint of heat resistance and solvent resistance.
- R 25 and R 26 each independently represent a hydrogen atom, a halo group or an alkyl group having 1 to 8 carbon atoms.
- R 11 ⁇ R 14, R 23 and R 24 have the same meanings as R 11 ⁇ R 14, R 23 and R 24 of the above formula (3) and (4).
- R 11 , R 12 , R 23 and R 24 are preferably alkyl groups having 1 to 6 carbon atoms, and R 13 is preferably 1 to 6 carbon atoms.
- An alkyl group, a cycloalkyl group having 3 to 6 carbon atoms, or a phenyl group is preferable.
- R 14 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- R 25 and R 26 are preferably a hydrogen atom, a halo group or an alkyl group having 1 to 6 carbon atoms.
- methine-based chromophore those represented by the following formulas (6-1) to (6-3) are preferable, and those represented by the following formula (6-1) are more preferable.
- R 31 represents a hydrogen atom or a halo group.
- R 32 , R 33 , R 34 and R 35 each independently represents an alkyl group having 1 to 6 carbon atoms.
- R 36 represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
- E represents —CH ⁇ CH—, —CH ⁇ CH—CH ⁇ , —CH ⁇ CH—NR 37 —, —CH ⁇ N—NR 37 — or —N ⁇ N—NR 37 —.
- R 37 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- R a represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group.
- halo group and the alkyl group having 1 to 6 carbon atoms are the same as those described above.
- substituent for the alkyl group include a halo group, a cyano group, and a hydroxyl group.
- the R a preferred is a group represented by the following formula (6a) ⁇ (6h), and more preferably a group represented by the following formula (6b) or (6h).
- R 38 and R 45 each independently represent an alkyl group having 1 to 6 carbon atoms.
- R 39 represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
- R 40 , R 42 , R 43 , R 44 , R 47 , R 48 and R 49 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- R 41 , R 46 and R 50 are each independently a hydrogen atom, a halo group, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or cyano. Indicates a group.
- the alkyl group in R 32 to R 50 is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
- the alkoxy group for R 41 , R 46 and R 50 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group.
- Representative examples of the cations represented by the above formulas (6-1) to (6-3) include cations represented by the following formulas.
- azo chromophore those represented by the following formulas (7-1) to (7-6) are preferable.
- R 51 , R 52 , R 53 , R 54 , R 55 and R 57 each independently represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
- R 56 and R 60 each independently represent a hydrogen atom, a halo group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group.
- R 58 represents an alkyl group having 1 to 6 carbon atoms.
- R 59 represents a group forming a quaternary ammonium.
- R b represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group.
- halo group the alkyl group having 1 to 6 carbon atoms
- alkoxy group having 1 to 6 carbon atoms are the same as those described above.
- substituent for the alkyl group include a halo group, a cyano group, and a hydroxyl group.
- R 74 R 75 Or a group represented by the following formula (7-i) or (7-ii).
- R 61 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- R 62 , R 63 and R 64 each independently represents an alkyl group having 1 to 6 carbon atoms
- R 74 and R 75 independently represents an alkyl group having 1 to 6 carbon atoms
- r represents an integer of 1 to 5 independently of each other.
- R 61 and r are as defined above.
- R b is preferably a group represented by the following formulas (7a) to (7e) or a substituted or unsubstituted phenyl group.
- R 65 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group.
- R 66 represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
- R 67 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
- R 68 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- R 69 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- R 70 to R 73 each independently represent a hydrogen atom, a halo group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group.
- halo group examples include a halo group, a hydroxyl group, a cyano group, and a —CONH 2 group.
- substituent of the phenyl group examples include a halo group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group, and a nitro group.
- Representative examples of the cations represented by the above formulas (7-1) to (7-6) include cations represented by the following formulas.
- diarylmethane chromophore those represented by the following formula (8-1) or (8-2) are preferable.
- R 81 , R 82 , R 83 , R 84 , R 86 , R 87 , R 88 and R 89 each independently represent an alkyl group having 1 to 6 carbon atoms.
- R 85 , R 90 and R 91 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- Representative examples of the cations represented by the above formulas (8-1) to (8-2) include cations represented by the following formulas.
- quinoneimine chromophore those represented by the following formulas (9-1) to (9-3) are preferable.
- R 101, R 102, R 103 , R 104, R 105, R 106, R 108, R 109, R 110, R 111, R 114, R 115, R 116, R 117 and R 118 are independently of one another ,
- R 107 and R 113 each independently represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms.
- R 112 represents —NR 119 R 120 , a hydroxyl group, a nitro group, or a cyano group.
- R 119 and R 120 each independently represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
- Q represents an oxygen atom or a sulfur atom.
- alkyl group having 1 to 6 carbon atoms examples include a halo group, a hydroxyl group, and a cyano group.
- anthraquinone chromophore those represented by the following formula (10-1) or (10-2) are preferable.
- R 131 , R 135 and R 136 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted phenyl group.
- R 132 , R 133 , R 134 , R 138 , R 139 and R 140 each independently represent an alkyl group having 1 to 6 carbon atoms.
- R 137 represents a methylene group or a substituted or unsubstituted alkanediyl group having 2 to 20 carbon atoms.
- alkyl group having 1 to 6 carbon atoms examples include a halo group, a hydroxyl group, and a cyano group.
- the phenyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.
- examples of the substituent of the alkanediyl group having 2 to 20 carbon atoms include a hydroxyl group, a cyano group, and a nitro group.
- phthalocyanine chromophore those represented by the following formula (11) are preferable.
- CuPc represents a copper phthalocyanine residue.
- T represents a group represented by the following formula (11a) or (11b). ]
- R 151 , R 152 , R 153 , R 154 , R 155 , R 156 , R 157 and R 158 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group.
- s independently represents an integer of 2 to 8.
- t represents an integer of 1 to 5 independently of each other.
- R 171 , R 172 , R 173 and R 174 each independently represent a hydrogen atom, —R 178 or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
- the hydrogen atom contained in the aromatic hydrocarbon group includes a halo group, —R 178 , —OH, —OR 178 , —SO 3 H, —SO 3 M, —CO 2 H, —CO 2 R 178 , It may be substituted with —SO 3 R 178 , —SO 2 NHR 179 or —SO 2 NR 179 R 180 .
- R 175 and R 176 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
- R 177 represents —SO 3 H, —SO 3 M, —CO 2 H, —CO 2 R 178 , —SO 3 R 178 , —SO 2 NHR 179 or —SO 2 NR 179 R 180 .
- u represents an integer of 0 to 5, and when u is an integer of 2 or more, a plurality of R 177 may be the same or different.
- R 178 represents a saturated hydrocarbon group having 1 to 10 carbon atoms. However, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halo group, and the saturated hydrocarbon group is a —O— group, —CO— group or —NR 178 between C—C bonds. -It may have a group.
- R 179 and R 180 are each independently a chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or —X, or R 179 and R 180 are bonded to each other.
- the hydrogen atom contained in the alkyl group and cycloalkyl group may be substituted with a hydroxyl group, a halo group, —X, —CH ⁇ CH 2, or —CH ⁇ CHR 178.
- the group may have an —O— group, —CO— group or —NR 178 — between the C—C bonds, and the hydrogen atom contained in the heterocyclic group may be —R 178 , —OH or — X may be substituted.
- M represents a sodium atom or a potassium atom.
- X represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms.
- the hydrogen atom contained in the aromatic hydrocarbon group and aromatic heterocyclic group is —OH, —R 178 , —OR 178 , —NO 2 , —CH ⁇ CH 2 , —CH ⁇ CHR 178 or a halo group. May be substituted. ]
- the saturated hydrocarbon group according to R 178 may be linear, branched or cyclic as long as it has 1 to 10 carbon atoms, and may have a bridged structure. Specific examples include saturated aliphatic hydrocarbon groups and saturated alicyclic hydrocarbon groups. Specific examples of the saturated aliphatic hydrocarbon group and the saturated alicyclic hydrocarbon group include those similar to the alkyl group and cycloalkyl group described above.
- heterocyclic group having 1 to 10 carbon atoms formed by combining R 179 and R 180 with each other examples include pyrrolidinyl, pyrazolinyl, morpholinyl, theomorpholinyl, piperidyl, piperidino, piperazinyl, homopiperazinyl, tetrahydro Pyrimidine group, 1,3-dioxolan-2-yl group, pyridyl group, pyrazinyl group, pyrimidyl group, pyridazinyl group, quinolyl group, isoquinolyl group, phthalazinyl group, quinoxalinyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, A thiazolyl group, a benzothiazolyl group, an oxazolyl group, an indolyl group, an indazolyl group, a benzoimidazolyl group, a
- Examples of the substituent of the heterocyclic group include a halo group, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an amino group, and an alkyl group having 1 to 6 carbon atoms.
- Examples of the aromatic heterocyclic group having 5 to 10 carbon atoms in X include furyl, thienyl, pyridyl, pyrrolyl, oxazolyl, isoxazol, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, pyrimidyl, etc. Can be mentioned.
- the aromatic hydrocarbon group according to R 171 , R 172 , R 173 , R 174 and X is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
- Examples of —SO 3 R 178 relating to R 171 , R 172 , R 173 , R 174 and R 177 include a methanesulfonyl group, an ethanesulfonyl group, a hexanesulfonyl group, and a decanesulfonyl group.
- Examples of —CO 2 R 178 include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, a butyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a methoxypropyloxycarbonyl group.
- R 179 and R 180 related to —SO 2 NHR 179 and —SO 2 NR 179 R 180 include a branched alkyl group having 6 to 8 carbon atoms, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, carbon An aralkyl group having 8 to 10 carbon atoms, an alkyl group having 2 to 8 carbon atoms substituted with a hydroxyl group or an alkoxy group, and an aryl group are preferable.
- R 171 , R 172 , R 173 and R 174 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or an ethyl group.
- R 175 and R 176 are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group preferably has 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
- R 177 is preferably —SO 3 H, —SO 3 M, —CO 2 H, or —CO 2 R 178, more preferably —CO 2 H or —CO 2 R 178 .
- R 178 in -CO 2 R 178 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, more preferably methyl or ethyl.
- u is preferably 1 or 2, and more preferably 1.
- cationic chromophores include, for example, cations represented by the following formula.
- the present colorant may have a structural unit other than the structural unit represented by the formula (1) (hereinafter also referred to as “other structural unit”), and examples of such a structural unit include: For example, a structural unit derived from an ethylenically unsaturated monomer having one or more carboxyl groups, a structural unit derived from an N-substituted maleimide, a structural unit derived from an aromatic vinyl compound, a (meth) acrylic acid ester A structural unit derived from the above, a structural unit derived from vinyl ether, a structural unit derived from a macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain, a structural unit represented by the following formula (2), etc. be able to.
- R 4 represents a hydrogen atom, a methyl group or a trifluoromethyl group
- R 5 and R 6 each independently represent a hydrogen atom, a halo group, or a substituted or unsubstituted hydrocarbon group.
- at least one of R 5 and R 6 is a halo group or a halo group-substituted hydrocarbon group.
- a 2 represents a divalent group
- G 2 represents a divalent hydrocarbon group or a single bond.
- the divalent hydrocarbon group may have a linking group selected from —O— group, —S— group, —CO— group, and —NR 8 — group between C—C bonds.
- R 8 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
- W n + represents a proton, a metal cation or an onium cation (excluding a cationic chromophore represented by Z m + ); n represents a natural number of 1 to 3, q represents a natural number of 1 to 8. ]
- R 4 has the same meaning as R 1 in formula (1)
- R 5 and R 6 have the same meanings as R 2 and R 3 in formula (1)
- a 2 is synonymous with A in Formula (1)
- G 2 is synonymous with G in Formula (1)
- R 8 has the same meaning as R 7 in formula (1).
- monovalent metal cations such as lithium ion, sodium ion, potassium ion and cesium ion
- divalent metal cations such as magnesium ion, calcium ion and barium ion
- trivalent metals such as aluminum ion Mention may be made of metal cations.
- Examples of the onium cation in W n + include ammonium ions and phosphonium ions.
- the structural unit derived from the ethylenically unsaturated monomer having one or more carboxyl groups is, for example, (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxy Ethyl], ⁇ -carboxypolycaprolactone mono (meth) acrylate, and ethylenically unsaturated monomers having a carboxyl group such as p-vinylbenzoic acid.
- a structural unit derived from N-substituted maleimide can be obtained by N-substituted maleimide such as N-phenylmaleimide and N-cyclohexylmaleimide.
- the aromatic vinyl compound can be obtained by an aromatic vinyl compound such as styrene, ⁇ -methylstyrene, p-hydroxystyrene, p-hydroxy- ⁇ -methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene, and the like.
- structural units derived from (meth) acrylic acid esters include, for example, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl ( (Meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2) ⁇ 10) Mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 ⁇ 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decane -8-I (Meth)
- the structural units derived from vinyl ether include, for example, cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- ( It can be obtained with a vinyl ether such as vinyloxymethyl) -3-ethyloxetane.
- the structural unit derived from a macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain is, for example, polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, or polysiloxane. It can be obtained by a macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain.
- the colorant preferably has a structural unit derived from (meth) acrylic acid ester as a structural unit and a structural unit represented by the formula (2).
- structural units derived from (meth) acrylic acid esters (meth) acrylic acid esters having at least one group selected from the group consisting of oxiranyl groups, oxetanyl groups, polymerizable unsaturated groups and blocked isocyanate groups It is more preferable to have a derived structural unit.
- Such compounds include allyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyl. And oxymethyl] -3-ethyloxetane and 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl (meth) acrylate.
- the copolymerization ratio of the structural units derived from (meth) acrylic acid esters is preferably 10 to 100 mol% with respect to the entire other structural units from the viewpoint of solvent resistance, and preferably 30 to 100 mol%. More preferred is mol%, and further more preferred is 50 to 100 mol%.
- the copolymerization ratio of the structural unit represented by the formula (2) is preferably 10 to 100 mol%, preferably 20 to 90 mol based on the whole other structural units from the viewpoint of solvent resistance. % Is more preferable, and 30 to 80 mol% is still more preferable.
- the colorant has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran), usually 1,000 to 100,000, preferably It is 3,000 to 50,000, more preferably 3,000 to 20,000.
- Mw polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography
- GPC gel permeation chromatography
- the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the colorant in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.
- Mn here is the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).
- the present colorant can be produced by a known method.
- the colorant thus obtained is soluble in various organic solvents such as propylene glycol monomethyl ether acetate and has excellent solvent resistance.
- the present colorant can be used alone or in admixture of two or more.
- the colored composition of the present invention can further contain another colorant as the colorant (A).
- the content ratio of the present colorant is preferably 0.1 to 99% by mass, more preferably 1 to 80% by mass, still more preferably 10 to 70% by mass, and particularly preferably 20% in the total colorant. ⁇ 60% by mass.
- colorants are not particularly limited, and colors and materials can be appropriately selected according to the use, and any of pigments, dyes, and natural pigments other than the present colorant can be used.
- organic pigments and organic dyes are preferable and organic pigments are more preferable in terms of obtaining pixels with high luminance and color purity.
- organic pigment examples include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), among which JP-A-2001-081348 and JP-A-2010. Lake pigments described in JP-A No. 026334, JP-A 2010-191304, JP-A 2010-237384, JP-A 2010-237369, JP-A 2011-006602, JP-A 2011-145346, etc. , C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment red 264, C.I. I.
- 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.
- a known dispersant and dispersion aid may be further contained.
- Known dispersants include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants.
- a dispersant, a polyester-based dispersant, an acrylic-based dispersant and the like, and examples of the dispersion aid include a pigment derivative and the like.
- 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, Disperbyk-2164 (above, BYK Chemy (BYK) 76), Lubrizol Co., Ltd.), polyethyleneimine dispersant, Solsperse 24000 (Lubrisol Co., Ltd.), polyester dispersion As, Adisper PB821, Adisper PB822, Adisper PB880, Adisper PB881 (or more, Ajinomoto Fine-Techno Co., Ltd.), and the like.
- pigment derivative examples include copper phthalocyanine, diketopyrrolopyrrole, quinophthalone sulfonic acid derivatives, and the like.
- colorants can be used alone or in admixture of two or more.
- the content ratio of the colorant is usually 5 in the solid content of the colored composition from the viewpoint of forming a pixel having high heat resistance and high brightness and excellent color purity, or a black matrix and black spacer excellent in light shielding properties. It is ⁇ 70% by mass, preferably 5 to 60% by mass. Moreover, it is preferable that the content rate of this coloring agent is 2 mass% or more in the solid content of a coloring composition, Furthermore, 3 mass% or more, It is especially 5 mass% or more.
- solid content is components other than the solvent mentioned later.
- the polymerizable compound refers to a compound having two or more polymerizable groups.
- the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group.
- the polymerizable compound is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.
- 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 polyfunctional (meta) modified with caprolactone. ) Acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting hydroxyl-functional (meth) acrylate and polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid anhydride
- the polyfunctional (meth) acrylate which has a carboxyl group obtained by making a product 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; and 3 such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of aliphatic polyhydroxy compounds having a valence higher than that.
- Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol dimethacrylate.
- 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.
- caprolactone-modified polyfunctional (meth) acrylates include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955.
- the polyfunctional (meth) acrylate modified with alkylene oxide is modified with at least one selected from bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide.
- Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure.
- the melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof.
- Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ′′, N ′′ -hexa (alkoxymethyl) melamine, N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril, and the like.
- polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethanes (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ′′, N ′′ -hexa (alkoxymethyl) melamine, N, N, N ′, N ′ -Tetra (alkoxymethyl) benzoguanamine is 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.
- (B) polymeric compound can be used individually or in mixture of 2 or more types.
- the content of the polymerizable compound (B) is preferably 10 to 1,000 parts by weight, more preferably 100 to 800 parts by weight, and further 200 to 700 parts by weight with respect to 100 parts by weight of the (A) colorant. Particularly preferred is 300 to 600 parts by mass.
- the colored composition of the present invention can contain a binder resin.
- a binder resin is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group.
- a polymer having a carboxyl group hereinafter referred to as “carboxyl group-containing polymer”.
- an ethylenically unsaturated monomer having one or more carboxyl groups hereinafter referred to as “unsaturated monomer”. (C1) ") and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as” unsaturated monomer (c2) ").
- Examples of the unsaturated monomer (c1) include those similar to the ethylenically unsaturated monomer having a carboxyl group. Moreover, an unsaturated monomer (c1) can be used individually or in mixture of 2 or more types.
- the unsaturated monomer (c2) includes, for example, N-substituted maleimide, aromatic vinyl compound, (meth) acrylic acid ester, vinyl ether, and a mono (meth) acryloyl group at the end of the polymer molecular chain.
- a macromonomer etc. can be mentioned, As a specific example, the same thing as the above-mentioned can be mentioned.
- an unsaturated monomer (c2) can be used individually or in mixture of 2 or more types.
- 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 (c1) and the unsaturated monomer (c2) 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 gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran), usually from 1,000 to 100,000. It is preferably 3,000 to 50,000.
- GPC gel permeation chromatography
- the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3. .0.
- Mn here is the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).
- 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 weight, preferably 50 to 800 parts by weight, more preferably 100 to 650 parts by weight with respect to 100 parts by weight of the colorant (A). More preferably, it is 200 to 500 parts by mass.
- the coloring composition of the present invention can contain a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition.
- the photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of the polymerizable compound (B) by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. .
- photopolymerization initiators examples include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, ⁇ -Diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds and the like.
- the photopolymerization initiators can be used alone or in admixture of two or more.
- the photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.
- thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.
- acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- And morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.
- biimidazole compound examples include 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, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 Examples include '5,5'-tetraphenyl-1,2'-biimidazole.
- a hydrogen donor in terms of improving sensitivity.
- the “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
- the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like.
- an amine-based hydrogen donor can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.
- triazine compounds include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) ) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -
- O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl.
- a sensitizer when using a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound, a sensitizer can be used in combination.
- a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl.
- Ethyl aminobenzoate 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.
- the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, with respect to 100 parts by mass of the polymerizable compound (B).
- the coloring composition of the present invention contains the components (A) and (B) and other components that are optionally added, but is usually prepared as a liquid composition by blending a solvent.
- a solvent as long as (A) and (B) component which comprise a coloring composition, and another component are disperse
- Ethylene glycol monomethyl ether for example 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
- 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 in the coloring composition is preferably 5 to 50% by mass, and preferably 10 to 40% by mass. Is more 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 colored cured film of the present invention is formed using the colored composition of the present invention. Specifically, each color pixel, black matrix, black spacer, etc. constituting the color filter Means.
- the colored cured film used for the color filter which comprises a display element and a solid-state image sensor, and its formation method are demonstrated.
- a method for producing a color filter first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, a blue liquid composition of the radiation-sensitive colored composition of the present invention is applied on the substrate, and then pre-baked to evaporate the solvent to form a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which blue pixel patterns (colored cured films) are arranged in a predetermined arrangement.
- each radiation sensitive coloring composition of green or red application of each radiation sensitive coloring composition, pre-baking, exposure, development, and post-baking are performed in the same manner as described above to obtain a green pixel array and red color.
- a color filter in which a pixel array of the three primary colors of blue, green and red is arranged on the substrate is obtained.
- the order of forming pixels of each color is not limited to the above.
- 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 photolithographic method. However, it is a radiation sensitive material in which a black colorant is dispersed.
- a colored composition can be used in the same manner as in the case of forming the pixel.
- 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 spraying, roll coating, spin coating (spin coating), slit die coating (slit coating), bar coating, etc.
- spin coating method 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 thereof 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.
- An ultraviolet LED can also be used as the exposure light source.
- the wavelength is preferably radiation in the range of 190 to 450 nm.
- the exposure dose of radiation is preferably 10 to 10,000 J / m 2 .
- the alkali developer include sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene.
- An aqueous solution of 1,5-diazabicyclo- [4.3.0] -5-nonene is preferable.
- a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like
- a surfactant such as methanol or ethanol
- it is usually washed with water after alkali development.
- a development processing method a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
- the development conditions are preferably 5 to 300 seconds at room temperature.
- the post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
- the film thickness of the pixel thus formed is usually 0.5 to 5 ⁇ m, preferably 1.0 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.
- a partition having a light shielding function is formed on the surface of the substrate.
- a liquid composition of a blue thermosetting coloring composition is discharged into the formed partition wall by an inkjet apparatus, and then prebaked to evaporate the solvent.
- the coating film is exposed as necessary, and then 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 the pixel patterns of the three primary colors of blue, green and red are arranged on the substrate is obtained.
- the order of forming pixels of each color is not limited to the above.
- the partition plays not only a light shielding function but also a function for preventing the color mixing of the thermosetting coloring compositions discharged in the respective sections, it is compared with the black matrix used in the first method described above.
- the film thickness is thick. Therefore, 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 as necessary on the pixel pattern thus obtained, 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 radiation-sensitive colored 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.
- the radiation-sensitive colored composition of the present invention can be suitably used in forming any colored cured film such as each color pixel, black matrix, and black spacer used in the color filter. Since the color filter including the colored cured film of the present invention formed in this way has extremely high luminance and color purity, it can be used in color liquid crystal display elements, color imaging tube elements, color sensors, organic EL display elements, electronic paper, and the like. Very useful. In addition, the display element mentioned later should just have at least 1 or more of colored cured films formed using the radiation sensitive coloring composition of this invention.
- the display element of this invention comprises the colored cured film of this 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 colored cured film of the present invention may be a transmissive type or a reflective type, and can take 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. Can be taken.
- TFT thin film transistor
- TFT thin film transistor
- ITO indium-doped indium oxide
- a structure can also be adopted.
- the latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.
- the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed, or on the substrate side on which the ITO electrode or IZO electrode is formed.
- the color liquid crystal display element comprising the colored cured film of the present invention can comprise 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 color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a 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
- the color liquid crystal display element having the colored cured film of the present invention includes TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Plane Switching) type, VA (Vertical Alignment) type, OCB (Optical) type.
- TN Transmission Nematic
- STN Super Twisted Nematic
- IPS In-Plane Switching
- VA Very Alignment
- OCB Optical
- An appropriate liquid crystal mode such as a Compensated Birefringence type can be applied.
- the organic EL display device having the colored cured film of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.
- the electronic paper provided with the colored cured film of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-2007-41169.
- a stirrer, thermometer, dropping funnel and reflux condenser were attached to a 300 mL four-necked flask containing a stir bar, water 100 g, sodium dithionite 14 g (0.080 mol), triethylamine 12.1 g (0.12 Mole).
- a solution of 9.56 g (0.040 mol) of 5-bromo-4,4,5,5-tetrafluoropentan-1-ol dissolved in 80 g of acetonitrile was added in 15 minutes. It was dripped. Next, the mixture was heated in an oil bath and reacted at an internal temperature of 60 ° C. for 5 hours under a nitrogen stream.
- reaction solution was cooled to 25 ° C. and allowed to stand for 15 minutes, whereby the reaction solution was separated into two layers.
- the organic layer was separated, 100 g of acetonitrile was further added to the aqueous layer, the organic layer was separated, combined with the previous organic layer, and concentrated under reduced pressure.
- the obtained residue was dried under reduced pressure at 40 ° C. to obtain 11.4 g (0.0350 mol, yield: 88%) of a viscous oily substance.
- solvent deuterated methanol
- a 300 mL three-necked flask was equipped with a stirrer, a thermometer, and a dropping funnel.
- the compound (1-b) obtained above and 50 mL of dichloromethane were added, and the mixture was cooled to 5 ° C. and stirred under a nitrogen stream. Thereafter, 4.33 g (0.043 mol) of triethylamine was added and stirred for a while, and 3.58 g (0.034 mol) of methacrylic acid chloride was added dropwise over 15 minutes. Thereafter, the internal temperature was heated to 25 ° C. and stirred for 6 hours.
- Monomer (1) 4.50 g, methyl methacrylate 5.50 g, ⁇ -thioglycerol 0.713 g, and cyclohexanone 20 g were mixed and dissolved uniformly. The solution was heated to 100 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, a solution prepared by dissolving 0.541 g of ⁇ , ⁇ '-azobisisobutyronitrile in 10.4 g of cyclohexanone was added dropwise over 30 minutes. After completion of the addition, the mixture was further stirred at the same temperature for 3 hours. Continued.
- the reaction solution was cooled to room temperature, 60 g of acetone was added to make a uniform solution, which was added dropwise to 1.1 L of hexane.
- the produced precipitate was collected by filtration and washed with hexane.
- the obtained solid was dried under reduced pressure at 50 ° C. to obtain 8.90 g of a polymer represented by the above structural formula.
- the resulting polymer had an Mw 7,900, Mn is 3,600, 1 H-NMR spectrum: 1 at a ratio of x and y by (a solvent deuterated acetone) measuring the molar ratio (x / y) /4.91 was confirmed. This is referred to as a polymer (1).
- thermometer and a dropping funnel were attached to a 300 mL three-necked flask containing a stir bar, and 23.0 g (0.220 mol) of methacrylic acid chloride and 160 mL of dichloromethane were added and dissolved uniformly in a nitrogen atmosphere.
- the solution was cooled to 0 ° C., 30.4 g (0.300 mol) of triethylamine was added, and the mixture was further stirred.
- 34.4 g (0.200 mol) of 2-iodoethanol was added dropwise over 30 minutes, and then the reaction solution was warmed to room temperature and stirred for 2 hours.
- reaction solution was poured into 300 mL of saturated aqueous ammonium chloride solution to separate the organic layer, and the aqueous layer was extracted twice with 200 mL of dichloromethane.
- the organic layers were combined, washed successively with 500 g of saturated aqueous sodium hydrogen carbonate solution and 500 g of saturated brine, and concentrated under reduced pressure.
- the obtained residue was dried at 30 ° C. under reduced pressure to obtain 44.6 g (0.186 mol, yield: 93%) of a viscous oily substance. It was confirmed by 1 H-NMR spectrum (solvent: deuterated chloroform) that the obtained compound was a compound represented by the above formula (2-a).
- thermometer and a dropping funnel were attached to a 300 mL three-necked flask containing a stirring bar, and 8.53 g (0.0250 mol) of compound (1-b) and 40 mL of dichloromethane were added. This was cooled to 20 ° C. and stirred. Next, 3.79 g (0.0375 mol) of triethylamine was added and stirred for a while. Next, 9.60 g (0.0400 mol) of the compound (2-a) was added dropwise over 15 minutes, and then the internal temperature was heated to 25 ° C. and stirred for 6 hours.
- reaction solution was poured into 100 g of water to separate the organic layer, and the aqueous layer was extracted with 100 g of dichloromethane. The organic layers were combined, washed three times with 150 g of water, and concentrated under reduced pressure. The obtained residue was purified by column chromatography to obtain 8.84 g (0.0195 mol, yield: 78%) of a viscous oily substance. It was confirmed by 1 H and 19 F-NMR spectrum (solvent: deuterated chloroform) that the obtained compound was a compound represented by the above formula. This is designated as monomer (2).
- a polymer represented by the above structural formula is obtained in the same manner as in Synthesis Example 1 except that 4.98 g of the monomer (2) is used instead of the monomer (1). 9.21 g of (2) was obtained.
- the obtained polymer (2) had an Mw of 7,100 and an Mn of 3,300, and the ratio of x to y was found to be a molar ratio (x / y) by measurement of 1 H-NMR spectrum (solvent: deuterated acetone). In y), it was confirmed to be 1 / 4.45.
- the polymer represented by the above structural formula was used in the same manner as in Synthesis Example 1 except that 2.39 g of vinyl sulfonic acid triethylamine salt was used instead of the monomer (1). 7.51 g of 3) was obtained.
- the obtained polymer (3) had an Mw of 8,200 and an Mn of 3,800, and a 1 H-NMR spectrum (solvent: deuterated acetone) measurement showed that the ratio of x to y was a molar ratio (x / In y), it was confirmed to be 1 / 4.66.
- Preparation Example 4 10 parts by mass of the polymer D and 90 parts by mass of propylene glycol monomethyl ether acetate were mixed to prepare a polymer solution (A-4).
- Preparation Example 5 10 parts by mass of polymer E and 90 parts by mass of propylene glycol monomethyl ether acetate were mixed to prepare a polymer solution (A-5).
- Preparation Example 6 10 parts by mass of the polymer F and 90 parts by mass of propylene glycol monomethyl ether acetate were mixed to prepare a polymer solution (A-6).
- Preparation Example 7 10 parts by mass of the polymer G and 90 parts by mass of propylene glycol monomethyl ether acetate were mixed to prepare a polymer solution (A-7).
- Synthesis example 8 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 (C1) This binder resin is referred to as “binder resin (C1)”.
- Example 1 13.5 parts by weight of the pigment dispersion (a-1) and 7.2 parts by weight of the colorant solution (A-1) as the colorant, (C) 30.0 parts by weight of the binder resin (C1) solution as the binder resin, B) 13.7 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as the polymerizable compound, and 2-benzyl-2- 1.8 parts by mass of dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals) and NCI-930 (produced by ADEKA) 0 1 part by weight, 0.05 part by weight of Megafac F-554 (manufactured by DIC Corporation) as a fluoro
- the coloring composition (S-1) was applied on a soda glass substrate on which a SiO 2 film for preventing elution of sodium ions was formed using a spin coater, and then a hot plate at 90 ° C. Was pre-baked for 2 minutes to form a coating film having a thickness of 2.5 ⁇ m. Next, after cooling the substrate to room temperature, each coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 400 J / m 2 through a photomask using a high-pressure mercury lamp.
- shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm 2 (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 200 ° C. for 30 minutes to form a dot pattern on the substrate.
- the coloring composition (S-1) was applied on a soda glass substrate on which a SiO 2 film for preventing elution of sodium ions was formed using a spin coater, and then heated at 90 ° C. The plate was pre-baked for 2 minutes to form a coating film having a thickness of 2.5 ⁇ m. Next, after cooling the substrate to room temperature, each coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 400 J / m 2 through a photomask using a high-pressure mercury lamp.
- shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm 2 (nozzle diameter: 1 mm). Thereafter, this substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 30 minutes to form a dot pattern on the substrate. Thereafter, the substrate was immersed in propylene glycol monomethyl ether acetate at 80 ° C. for 40 minutes.
- Examples 2-6 and Comparative Examples 1-2 A colored composition was prepared in the same manner as in Example 1 except that the type and amount of the colorant and the binder resin solution were changed as shown in Table 1 in Example 1. Then, the obtained colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
Abstract
Description
したがって、本発明の課題は、耐熱性と耐溶剤性を両立できる着色硬化膜の形成に好適な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硬化膜、及びそれを具備する表示素子を提供することにある。
R1は、水素原子、メチル基又はトリフルオロメチル基を示し、
R2及びR3は、相互に独立に、水素原子、ハロ基、又は置換若しくは非置換の炭化水素を示す。但し、R2及びR3のうち少なくとも1つは、ハロ基又はハロ基置換炭化水素基である。
Aは、2価の基を示し、
Gは、2価の炭化水素基又は単結合を示す。但し、2価の炭化水素基は、C-C結合間に-O-基、-S-基、-CO-基、-NR7-基から選ばれる連結基を有していてもよい。R7は、水素原子、又は置換若しくは非置換の炭化水素基を示す。
Zm+は、カチオン性発色団を示し、
mは、1~3の自然数を示し、
pは、1~8の自然数を示す。〕
したがって、本発明の着色組成物は、カラー液晶表示素子、有機EL表示素子、電子ペーパー等の表示素子、CMOSイメージセンサ等の固体撮像素子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詳細に説明する。
本発明の着色組成物は、着色剤として本着色剤を含有する。本着色剤は、下記式(1)で表される構造単位を有する化合物であり、該化合物は、末端にSO3-基を有するアニオン部と、発色団を構成するカチオン部が塩を形成するものである。
R1は、水素原子、メチル基又はトリフルオロメチル基を示し、
R2及びR3は、相互に独立に、水素原子、ハロ基、又は置換若しくは非置換の炭化水素基を示す。但し、R2及びR3のうち少なくとも1つは、ハロ基又はハロ基置換炭化水素基である。
Aは、2価の基を示し、
Gは、2価の炭化水素基又は単結合を示す。但し、2価の炭化水素基は、C-C結合間に-O-基、-S-基、-CO-基、-NR7-基から選ばれる連結基を有していてもよい。R7は、水素原子、又は置換若しくは非置換の炭化水素基を示す。
Zm+は、カチオン性発色団を示し、
mは、相互に独立に、1~3の自然数を示し、
pは、1~8の自然数を示す。〕
R2、R3及びR7に係る炭化水素基としては、直鎖、分岐鎖及び環状のいずれでもよく、また橋かけ構造を有していてもよい。具体的には、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基が挙げられる。また、該炭化水素基は、飽和炭化水素基でも不飽和炭化水素基でもよく、不飽和結合を分子内及び末端のいずれに有していてもよい。
脂肪族炭化水素基としては、アルキル基が好ましく、アルキル基の炭素数は1~20が好ましく、1~12がより好ましく、1~6が更に好ましい。具体例としては、メチル基、エチル基、イソプロピル基、プロピル基、ブチル基、2-ブチル基、t-ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等が挙げられる。
脂環式炭化水素としては、シクロアルキル基が好ましく、シクロアルキル基の炭素数は3~20が好ましく、3~12がより好ましく、3~6が更に好ましい。具体例としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基等を挙げることができる。
芳香族炭化水素基としては、アリール基、アラルキル基が好ましく、アリール基の炭素数は6~20が好ましく、6~10がより好ましく、またアラルキル基の炭素数が7~20が好ましく、7~16がより好ましい。ここで、本明細書において「アリール基」とは、単環~3環式芳香族炭化水素基をいい、例えば、フェニル基、ナフチル基、ビフェニル基、アントラニル基等が挙げられる。アラルキル基の具体例としては、ベンジル基、フェネチル基、α-メチルベンジル基、2-フェニルプロパン-2-イル基等が挙げられる。
炭化水素基が有する置換基としては、ハロ基、水酸基、炭素数1~6のアルコキシ基等が挙げられ、炭化水素基が脂環式炭化水素基、芳香族炭化水素基である場合、置換基として炭素数1~6のアルキル基を有することもできる。ハロ基、炭素数1~6のアルキル基の具体例としては、前述と同様のものが挙げられる。炭素数1~6のアルコキシ基の具体例としては、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、ペンチルオキシ基等を挙げることができる。中でも、炭化水素基の置換基としては、ハロ基が好ましく、フッ素原子が更に好ましい。
なお、R2及びR3のうち少なくとも1つは、ハロ基又はハロ基置換炭化水基であるが、R2及びR3は、ともにハロ基であることが好ましく、ともにフッ素原子であることが更に好ましい。
また、R7としては、水素原子又は炭素数1~6のアルキル基が好ましく、該アルキル基は、フッ素原子で置換されていてもよい。
2価の脂肪族炭化水素基としては、例えば、アルカンジイル基、アルケンジイル基が挙げられ、その炭素数は、1~20が好ましく、2~12がより好ましく、2~6が更に好ましい。具体例としては、メチレン基、エタン-1,1-ジイル基、エタン-1,2-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、2-メチルプロパン-1,2-ジイル基、2,2-ジメチルプロパン-1,3-ジイル基、エテン-1,1-ジイル基、エテン-1,2-ジイル基、プロペン-1,2-ジイル基、プロペン-1,3-ジイル基、プロペン-2,3-ジイル基、1-ブテン-1,2-ジイル基、1-ブテン-1,3-ジイル基、1-ブテン-1,4-ジイル基、2-ペンテン-1,5-ジイル基、3-ヘキセン-1,6-ジイル基等を挙げることができる。
2価の脂環式炭化水素基としては、例えば、シクロアルキレン基、シクロアルケニレン基が挙げられ、その炭素数は、3~20が好ましく、3~12が更に好ましい。具体例としては、シクロプロピレン基、シクロブチレン基、シクロペンチレン基、シクロブテニレン基、シクロペンテニレン基、シクロヘキセニレン基等の単環式炭化水素環基、1,4-ノルボルニレン基、2,5-ノルボルニレン基等のノルボルニレン基、1,5-アダマンチレン基、2,6-アダマンチレン基等の架橋環式炭化水素環基等を挙げることができる。
中でも、Gに係る2価の炭化水素基としては、アルカンジイル基が好ましい。なお、Gに係る2価の炭化水素基は、C-C結合間に-O-基、-S-基、-CO-基、-NR7-基から選ばれる連結基を有してもよく、該連結基の結合位置は任意である。
pは、1~8の自然数を示すが、1~6の自然数が好ましく、2~6の自然数が更に好ましい。
Zm+は、カチオン性発色団である。Zm+に係るカチオン性発色団としては、前述のアニオン部とともに塩基性着色剤を形成し得るカチオンであれば特に限定されるものではないが、可視光領域に吸収極大を有するものが好ましく、360nm~830nmに吸収極大を有するものがより好ましく、380nm~780nmに吸収極大を有するものが更に好ましい。このようなカチオン性発色団としては、例えば、トリアリールメタン系発色団、メチン系発色団、アゾ系発色団、ジアリールメタン系発色団、キノンイミン系発色団、アントラキノン発色団、フタロシアニン系発色団、キサンテン系発色団等を挙げることができる。
Arは、置換又は非置換の芳香族炭化水素基を示す。
R11~R14は、相互に独立に、水素原子、炭素数1~8のアルキル基、炭素数3~8のシクロアルキル基、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。
R15~R22は、水素原子、炭素数1~8のアルキル基、-COOR'又はハロ基を示す。但し、R'は、水素原子又は炭素数1~8のアルキル基を示す。
Yは、水素原子又は下記式(4)で表される基を示す。〕
R11~R24(R15~R22に係る-COOR'のR'を含む)における炭素数1~8のアルキル基は直鎖でも分岐鎖でもよく、具体例としては、前述と同様のものを挙げることができる。中でも、炭素数1~6のアルキル基が好ましく、炭素数1~4のアルキル基がより好ましく、メチル基又はエチル基が特に好ましい。
R11~R14に係る炭素数3~8のシクロアルキル基の具体例としては、前述と同様のものを挙げることができる。中でも、炭素数3~6のシクロアルキル基が好ましく、シクロヘキシル基が特に好ましい。
R11~R14に係るエチレン性不飽和結合を有する基としては、例えば、ビニル基、プロペニル基、スチリル基、(メタ)アクリロイルオキシエチル基、(メタ)アクリロイルオキシプロピル基、(メタ)アクリロイルアミドエチル基、(メタ)アクリロイルアミドプロピル基等を挙げることができる。
R15~R22に係るハロ基の具体例としては、前述と同様のものを挙げることができる。中でも、塩素原子が好ましい。
R25及びR26は、相互に独立に、水素原子、ハロ基又は炭素数1~8のアルキル基を示す。
R11~R14、R23及びR24は、上記式(3)及び(4)に係るR11~R14、R23及びR24と同義である。〕
R31は、水素原子又はハロ基を示す。
R32、R33、R34及びR35は、相互に独立に、炭素数1~6のアルキル基を示す。
R36は、置換又は非置換の炭素数1~6のアルキル基を示す。
Eは、-CH=CH-、-CH=CH-CH=、-CH=CH-NR37-、-CH=N-NR37-又は-N=N-NR37-を示す。但し、R37は、水素原子又は炭素数1~6のアルキル基を示す。
Raは、置換若しくは非置換の芳香族炭化水素基、又は置換若しくは非置換の複素環基を示す。〕
Raとしては、下記式(6a)~(6h)で表される基が好ましく、下記式(6b)又は(6h)で表される基がより好ましい。
R38及びR45は、相互に独立に、炭素数1~6のアルキル基を示す。
R39は、置換又は非置換の炭素数1~6のアルキル基を示す。
R40、R42、R43、R44、R47、R48及びR49は、相互に独立に、水素原子又は炭素数1~6のアルキル基を示す。
R41、R46及びR50は、相互に独立に、水素原子、ハロ基、炭素数1~6のアルコキシ基、置換若しくは非置換の炭素数1~6のアルキル基、ニトロ基、水酸基又はシアノ基を示す。〕
中でも、R32~R50におけるアルキル基は、炭素数1~4のアルキル基が好ましく、メチル基又はエチル基がより好ましい。また、R41、R46及びR50におけるアルコキシ基としては、炭素数1~4のアルコキシ基が好ましく、メトキシ基又はエトキシ基がより好ましい。
R51、R52、R53、R54、R55及びR57は、相互に独立に、置換若しくは非置換の炭素数1~6のアルキル基を示す。
R56及びR60は、相互に独立に、水素原子、ハロ基、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、ニトロ基、水酸基又はシアノ基を示す。
R58は、炭素数1~6のアルキル基を示す。
R59は、4級アンモニウムを形成する基を示す。
Rbは、置換若しくは非置換の芳香族炭化水素基、又は置換若しくは非置換の複素環基を示す。〕
ここで、R61は、水素原子又は炭素数1~6のアルキル基を示し、R62、R63及びR64は、相互に独立に、炭素数1~6のアルキル基を示し、R74及びR75は、相互に独立に、炭素数1~6のアルキル基を示し、rは、相互に独立に、1~5の整数を示す。
R65は、水素原子、炭素数1~6のアルキル基、フェニル基又はベンジル基を示す。
R66は、水素原子又は置換若しくは非置換の炭素数1~6のアルキル基を示す。
R67は、水素原子、炭素数1~6のアルキル基又はフェニル基を示す。
R68は、水素原子又は炭素数1~6のアルキル基を示す。
R69は、水素原子又は炭素数1~6のアルキル基を示す。
R70~R73は、相互に独立に、水素原子、ハロ基、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、ニトロ基、水酸基又はシアノ基を示す。〕
R81、R82、R83、R84、R86、R87、R88及びR89は、相互に独立に、炭素数1~6のアルキル基を示す。
R85、R90及びR91は、相互に独立に、水素原子又は炭素数1~6のアルキル基を示す。〕
R101、R102、R103、R104、R105、R106、R108、R109、R110、R111、R114、R115、R116、R117及びR118は、相互に独立に、水素原子、置換若しくは非置換の炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、フェニル基又はベンジル基を示す。
R107及びR113は、相互に独立に、炭素数1~6のアルキル基又は炭素数6~20のアリール基を示す。
R112は、-NR119R120、水酸基、ニトロ基又はシアノ基を示す。但し、R119及びR120は、相互に独立に、置換又は非置換の炭素数1~6のアルキル基を示す。
Qは、酸素原子又は硫黄原子を示す。〕
R131、R135及びR136は、相互に独立に、水素原子、置換若しくは非置換の炭素数1~6のアルキル基、又は置換若しくは非置換のフェニル基を示す。
R132、R133、R134、R138、R139及びR140は、相互に独立に、炭素数1~6のアルキル基を示す。
R137は、メチレン基又は置換若しくは非置換の炭素数2~20のアルカンジイル基を示す。〕
CuPcは、銅フタロシアニン残基を示す。
Tは、下記式(11a)又は(11b)で表される基を示す。〕
R151、R152、R153、R154、R155、R156、R157及びR158は、相互に独立に、水素原子、炭素数1~6のアルキル基又はフェニル基を示す。
sは、相互に独立に、2~8の整数を示す。
tは、相互に独立に、1~5の整数を示す。〕
R171、R172、R173及びR174は、相互に独立に、水素原子、-R178又は炭素数6~10の芳香族炭化水素基を示す。但し、該芳香族炭化水素基に含まれる水素原子は、ハロ基、-R178、-OH、-OR178、-SO3H、-SO3M、-CO2H、-CO2R178、-SO3R178、-SO2NHR179又は-SO2NR179R180で置換されていてもよい。
R175及びR176は、相互に独立に、水素原子又は炭素数1~8のアルキル基を示す。
R177は、-SO3H、-SO3M、-CO2H、-CO2R178、-SO3R178、-SO2NHR179又は-SO2NR179R180を示す。
uは、0~5の整数を示し、uが2以上の整数である場合、複数のR177は、同一であっても異なっていてもよい。
R178は、炭素数1~10の飽和炭化水素基を示す。但し、該飽和炭化水素基に含まれる水素原子は、ハロ基で置換されていてもよく、また飽和炭化水素基は、C-C結合間に-O-基、-CO-基又は-NR178-基を有していてもよい。
R179及びR180は、相互に独立に、炭素数1~10の鎖状のアルキル基、炭素数3~30のシクロアルキル基又は-Xを示すか、あるいはR179及びR180が互いに結合して形成される炭素数1~10の置換若しくは非置換の複素環基を示す。但し、該アルキル基及びシクロアルキル基に含まれる水素原子は、水酸基、ハロ基、-X、-CH=CH2又は-CH=CHR178で置換されていてもよく、また該アルキル基及びシクロアルキル基は、C-C結合間に-O-基、-CO-基又は-NR178-を有していてもよく、該複素環基に含まれる水素原子は、-R178、-OH又は-Xで置換されていてもよい。
Mは、ナトリウム原子又はカリウム原子を示す。
Xは、炭素数6~10の芳香族炭化水素基、又は炭素数5~10の芳香族複素環基を示す。但し、該芳香族炭化水素基及び芳香族複素環基に含まれる水素原子は、-OH、-R178、-OR178、-NO2、-CH=CH2、-CH=CHR178又はハロ基で置換されていてもよい。〕
R171、R172、R173、R174及びR177に係る-SO3R178としては、メタンスルホニル基、エタンスルホニル基、ヘキサンスルホニル基、デカンスルホニル基等が挙げられる。また、-CO2R178としては、メチルオキシカルボニル基、エチルオキシカルボニル基、プロピルオキシカルボニル基、イソプロピルオキシカルボニル基、ブチルオキシカルボニル基、シクロヘキシルオキシカルボニル基、メトキシプロピルオキシカルボニル基等が挙げられる。更に、-SO2NHR179、-SO2NR179R180に係るR179、R180としては、炭素数6~8の分枝アルキル基、炭素数5~7の脂環式炭化水素基、炭素数8~10のアラルキル基、水酸基又はアルコキシ基で置換された炭素数2~8のアルキル基、アリール基が好ましい。
R175及びR176としては、水素原子又は炭素数が1~6のアルキル基が好ましく、該アルキル基の炭素数は1~4がより好ましく、メチル基又はエチル基が更に好ましい。
R177としては、-SO3H、-SO3M、-CO2H、又は-CO2R178が好ましく、-CO2H、又は-CO2R178がより好ましい。-CO2R178におけるR178は、炭素数が1~6のアルキル基が好ましく、炭素数が1~4のアルキル基がより好ましく、メチル基又はエチル基が更に好ましい。
uは、1又は2が好ましく、1がより好ましい。
R4は、水素原子、メチル基又はトリフルオロメチル基を示し、
R5及びR6は、相互に独立に、水素原子、ハロ基、又は置換若しくは非置換の炭化水素基を示す。但し、R5及びR6のうち少なくとも1つは、ハロ基又はハロ基置換炭化水素基である。
A2は、2価の基を示し、
G2は、2価の炭化水素基又は単結合を示す。但し、2価の炭化水素基は、C-C結合間に-O-基、-S-基、-CO-基、-NR8-基から選ばれる連結基を有していてもよい。R8は、水素原子、又は置換若しくは非置換の炭化水素基を示す。
Wn+は、プロトン、金属カチオン又はオニウムカチオン(但しZm+で表されるカチオン性発色団を除く。)を示し、
nは、1~3の自然数を示し、
qは、1~8の自然数を示す。〕
R5及びR6は、式(1)におけるR2及びR3と同義であり、
A2は、式(1)におけるAと同義であり、
G2は、式(1)におけるGと同義であり、
R8は、式(1)におけるR7と同義である。
Wn+における金属カチオンとしては、リチウムイオン、ナトリウムイオン、カリウムイオン、セシウムイオン等の1価の金属カチオン、マグネシウムイオン、カルシウムイオン、バリウムイオン等の2価の金属カチオン、アルミニウムイオン等の3価の金属カチオンを挙げることができる。
Wn+におけるオニウムカチオンとしては、アンモニウムイオン、ホスホニウムイオン等を挙げることができる。
また、芳香族ビニル化合物は、例えば、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により得ることができる。
また、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に由来する構造単位は、例えば、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により得ることができる。
(メタ)アクリル酸エステルに由来する構造単位の中では、オキシラニル基、オキセタニル基、重合性不飽和基及びブロックイソシアネート基よりなる群から選ばれる少なくとも1種の基を有する(メタ)アクリル酸エステルに由来する構造単位を有することがより好ましい。このような化合物としては、アリル(メタ)アクリレート、グリシジル(メタ)アクリレート、3,4-エポキシシクロヘキシルメチル(メタ)アクリレート、3-〔(メタ)アクリロイルオキシメチル〕オキセタン、3-〔(メタ)アクリロイルオキシメチル〕-3-エチルオキセタン、2-(0-[1'-メチルプロピリデンアミノ]カルボキシアミノ)エチル(メタ)アクリレート等を挙げることができる。
即ち、本着色剤の全構造単位中の式(1)で表される構造単位の合計割合xと、他の構造単位の割合yは、モル比で、x/y=1/0.5~1/19であることが好ましく、x/y=1/1.5~1/9がより好ましく、x/y=1/2~1/7が更に好ましい。
他の構造単位のうち、(メタ)アクリル酸エステルに由来する構造単位の共重合割合は、耐溶剤性の観点から、他の構造単位全体に対して10~100モル%が好ましく、30~100モル%がより好ましく、50~100モル%が更に好ましい。
他の構造単位のうち、式(2)で表される構造単位の共重合割合は、耐溶剤性の観点から、他の構造単位全体に対して10~100モル%が好ましく、20~90モル%がより好ましく、30~80モル%が更に好ましい。
本発明において重合性化合物とは、2個以上の重合可能な基を有する化合物をいう。重合可能な基としては、例えば、エチレン性不飽和基、オキシラニル基、オキセタニル基、N-アルコキシメチルアミノ基等を挙げることができる。本発明において、重合性化合物としては、2個以上の(メタ)アクリロイル基を有する化合物、又は2個以上のN-アルコキシメチルアミノ基を有する化合物が好ましい。
本発明において、(B)重合性化合物は、単独で又は2種以上を混合して使用することができる。
本発明の着色組成物には、バインダー樹脂を含有せしめることができる。これにより、着色組成物のアルカリ可溶性、基板への結着性、保存安定性等を高めることができる。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(c1)」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(c2)」という。)との共重合体を挙げることができる。
本発明の着色組成物には、光重合開始剤を含有せしめることができる。これにより、着色組成物に感放射線性を付与することができる。本発明に用いる光重合開始剤は、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、(B)重合性化合物の重合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、(A)及び(B)成分、並びに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。
溶媒としては、着色組成物を構成する(A)及び(B)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等を挙げることができる。
本発明の着色硬化膜は、本発明の着色組成物を用いて形成されたものであり、具体的には、カラーフィルタを構成する各色画素、ブラックマトリックス、ブラックスペーサー等を意味する。
カラーフィルタを製造する方法としては、第一に次の方法が挙げられる。まず、基板の表面上に、必要に応じて、画素を形成する部分を区画するように遮光層(ブラックマトリックス)を形成する。次いで、この基板上に、例えば、青色の本発明の感放射線性着色組成物の液状組成物を塗布したのち、プレベークを行って溶媒を蒸発させ、塗膜を形成する。次いで、この塗膜にフォトマスクを介して露光したのち、アルカリ現像液を用いて現像して、塗膜の未露光部を溶解除去する。その後、ポストベークすることにより、青色の画素パターン(着色硬化膜)が所定の配列で配置された画素アレイを形成する。
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、アルカリ現像液としては、例えば、炭酸ナトリウム、炭酸水素ナトリウム、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1.0~3μm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。
このようにして形成された本発明の着色硬化膜を含むカラーフィルタは、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。なお、後述する表示素子は、本発明の感放射線性着色組成物を用いて形成された着色硬化膜を少なくとも1以上具備するものであればよい。
本発明の表示素子は、本発明の着色硬化膜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。
本発明の着色硬化膜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、適宜の構造を採ることができる。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採ることができる。また、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)電極を形成した基板とが、液晶層を介して対向した構造を採ることもできる。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。なお、後者の構造を採用する場合、ブラックマトリックスやブラックスペーサーは、カラーフィルタを形成した基板側、並びにITO電極あるいはIZO電極を形成した基板側のどちらに形成されていても良い。
また、本発明の着色硬化膜を具備する電子ペーパーは、適宜の構造をとることが可能であり、例えば、特開2007-41169号公報に開示されている構造を挙げることができる。
合成例1
〔単量体(1)の合成〕
下記スキームにしたがって、下記の手順により単量体(1)を合成した。
下記スキームにしたがって、下記の手順により化合物Aを合成した。
〔単量体(2)の合成〕
下記スキームにしたがって、下記の手順により単量体(2)を合成した。
〔重合体(3)の合成〕
下記スキームにしたがって、下記の手順により化合物Cを合成した。
〔重合体(4)の合成〕
〔重合体(5)の合成〕
〔化合物Fの合成〕
〔化合物Gの合成〕
下記スキームにしたがって、下記の手順により染料Aを合成した。
調製例1
化合物Aを10質量部と、プロピレングリコールモノメチルエーテルアセテート90質量部とを混合し、着色剤溶液(A-1)を調製した。
化合物Bを10質量部と、プロピレングリコールモノメチルエーテルアセテート90質量部とを混合し、着色剤溶液(A-2)を調製した。
化合物Cを10質量部と、プロピレングリコールモノメチルエーテルアセテート90質量部とを混合し、着色剤溶液(A-3)を調製した。
重合体Dを10質量部と、プロピレングリコールモノメチルエーテルアセテート90質量部とを混合し、重合体溶液(A-4)を調製した。
重合体Eを10質量部と、プロピレングリコールモノメチルエーテルアセテート90質量部とを混合し、重合体溶液(A-5)を調製した。
重合体Fを10質量部と、プロピレングリコールモノメチルエーテルアセテート90質量部とを混合し、重合体溶液(A-6)を調製した。
重合体Gを10質量部と、プロピレングリコールモノメチルエーテルアセテート90質量部とを混合し、重合体溶液(A-7)を調製した。
染料Aを10質量部と、プロピレングリコールモノメチルエーテルアセテート90質量部とを混合し、染料溶液(A)を調製した。
合成例8
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が12,200、Mnが6,500であった。このバインダー樹脂を「バインダー樹脂(C1)」とする。
調製例9
着色剤としてC.I.ピグメントブルー15:6/C.I.ピグメントバイオレット23=80/20(質量比)の混合物12質量部、分散剤としてBYK2001(Disperbyk :ビックケミー(BYK)社製)3.8質量部(固形分換算)、ソルスパース12000:0.8質量部、及び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83.4質量部を、ビーズミルにより処理して顔料分散液(a-1)を調製した。
実施例1
着色剤として顔料分散液(a-1)13.5質量部及び着色剤溶液(A-1)7.2質量部、(C)バインダー樹脂としてバインダー樹脂(C1)溶液30.0質量部、(B)重合性化合物として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(日本化薬株式会社製、商品名KAYARAD DPHA)を13.7質量部、光重合開始剤として2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)ブタン-1-オン(商品名イルガキュア369、チバ・スペシャルティー・ケミカルズ社製)を1.8質量部及びNCI-930(株式会社ADEKA社製)0.1質量部、フッ素系界面活性剤としてメガファックF-554(DIC株式会社製)0.05質量部、及び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を混合して、固形分濃度20質量%の着色組成物(S-1)を調製した。
着色組成物(S-1)を、ナトリウムイオンの溶出を防止するSiO2膜が表面に形成されたソーダガラス基板上に、スピンコーターを用いて塗布した後、90℃のホットプレートで2分間プレベークを行って、膜厚2.5μmの塗膜を形成した。
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、フォトマスクを介して、各塗膜に365nm、405nm及び436nmの各波長を含む放射線を400J/m2の露光量で露光した。その後、これらの基板に対して、23℃の0.04質量%水酸化カリウム水溶液からなる現像液を現像圧1kgf/cm2(ノズル径1mm)で吐出することにより、90秒間シャワー現像を行った。その後、この基板を超純水で洗浄し、風乾した後、更に200℃のクリーンオーブン内で30分間ポストベークを行うことにより、基板上にドットパターンを形成した。
得られたドットパターンについて、カラーアナライザー(大塚電子(株)製MCPD2000)を用い、C光源、2度視野にて、CIE表色系における色度座標値(x,y)及び刺激値(Y)を測定した。
次いで、上記基板を230℃で90分間追加ベークをした後に、色度座標値(x,y)及び刺激値(Y)を測定し、追加ベーク前後での色変化、即ちΔE* abを評価した。その結果、ΔE* abの値が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。評価結果を表1に示す。なお、ΔE* ab値が小さい程、耐熱性が良好であると言える。
着色組成物(S-1)を、ナトリウムイオンの溶出を防止するSiO2膜が表面に形成されたソーダガラス基板上に、スピンコーターを用いて塗布した後、90℃のホットプレートで2分間プレベークを行って、膜厚2.5μmの塗膜を形成した。
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、フォトマスクを介して、各塗膜に365nm、405nm及び436nmの各波長を含む放射線を400J/m2の露光量で露光した。その後、これらの基板に対して、23℃の0.04質量%水酸化カリウム水溶液からなる現像液を現像圧1kgf/cm2(ノズル径1mm)で吐出することにより、90秒間シャワー現像を行った。その後、この基板を超純水で洗浄し、風乾した後、更に230℃のクリーンオーブン内で30分間ポストベークを行うことにより、基板上にドットパターンを形成した。その後、上記基板を、80℃のプロピレングリコールモノメチルエーテルアセテートに40分浸漬した。
浸漬前後の色度座標値(x、y)及び刺激値(Y)を測定し、浸漬前後での色変化、即ちΔE* abを評価した。その結果、ΔE* abの値が1.5未満の場合を「◎」、1.5以上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。評価結果を表1に示す。なお、ΔE* ab値が小さい程、耐溶剤性が良好であると言える。
実施例1において、着色剤並びにバインダー樹脂溶液の種類及び量を表1に示すように変更した以外は、実施例1と同様にして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1に示す。
Claims (5)
- (A)着色剤及び(B)重合性化合物を含む着色組成物であって、
前記着色剤が、下記式(1)で表される構造単位を有する化合物を含有する、着色組成物。
R1は、水素原子、メチル基又はトリフルオロメチル基を示し、
R2及びR3は、相互に独立に、水素原子、ハロ基、又は置換若しくは非置換の炭化水素基を示す。但し、R2及びR3のうち少なくとも1つは、ハロ基又はハロ基置換炭化水素基である。
Aは、2価の基を示し、
Gは、2価の炭化水素基又は単結合を示す。但し、2価の炭化水素基は、C-C結合間に-O-基、-S-基、-CO-基、-NR7-基から選ばれる連結基を有していてもよい。R7は、水素原子、又は置換若しくは非置換の炭化水素基を示す。
Zm+は、カチオン性発色団を示し、
mは、1~3の自然数を示し、
pは、1~8の自然数を示す。〕 - 前記Aが-O-基、-(CO)O-基、-O(CO)-基、-CO-基、-CONH-基、又は-SO2-基である、請求項1に記載の着色組成物。
- 更に(C)バインダー樹脂を含む、請求項1又は2に記載の着色組成物。
- 請求項1~3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硬化膜。
- 請求項4に記載の着色硬化膜を具備する表示素子。
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JP2017083505A (ja) * | 2015-10-23 | 2017-05-18 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
WO2018198919A1 (ja) * | 2017-04-28 | 2018-11-01 | 山本化成株式会社 | 化合物およびこれを用いたインキ |
JP2019011456A (ja) * | 2017-03-13 | 2019-01-24 | Jsr株式会社 | 着色組成物、着色硬化膜、カラーフィルタ、表示素子、受光素子、発光素子及び化合物 |
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