CN104570600A - Coloring composition, colored cured film and display device - Google Patents

Coloring composition, colored cured film and display device Download PDF

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CN104570600A
CN104570600A CN201410575556.3A CN201410575556A CN104570600A CN 104570600 A CN104570600 A CN 104570600A CN 201410575556 A CN201410575556 A CN 201410575556A CN 104570600 A CN104570600 A CN 104570600A
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coloring composition
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CN104570600B (en
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米田英司
仓怜史
山口紫
伊藤淳史
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JSR Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C09K19/322—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/542—Macromolecular compounds
    • 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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Abstract

The invention relates to a coloring composition, a colored cured film and a display device. The invention provides a coloring composition suitable for forming a colored cured film with excellent thermal resistance. The coloring composition contains (A) a coloring agent and (B) a coloring composition of a polymerized compound, and further contains (C2) any one or more of polymers of structures represented by the following formulas (2), (3), (4) or (5).

Description

Coloring composition, colored cured film, and display element
Technical Field
The present invention relates to a coloring composition, a colored cured film, and a display element, and more particularly, to a coloring composition for forming a colored cured film used for a transmissive or reflective color liquid crystal display element, a solid-state imaging element, an organic EL display element, electronic paper, or the like, a colored cured film formed using the coloring composition, and a display element provided with the colored cured film.
Background
In the production of color filters using colored radiation-sensitive compositions, there is known a method in which a pigment-dispersed colored radiation-sensitive composition is applied to a substrate and dried, and then the dried coating film is exposed to radiation in a desired pattern shape (hereinafter referred to as "exposure") and developed to obtain pixels of each color (see, for example, patent documents 1 to 2). Further, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed is also known (for example, see patent document 3). Further, a method of obtaining pixels of each color by an ink jet method using a pigment dispersion type colored resin composition is also known (for example, see patent document 4).
In recent years, there has been a strong demand for higher contrast of liquid crystal display elements and higher definition of solid-state imaging elements, and in order to achieve these demands, a technique using a dye as a colorant has been studied, but in general, when a dye is used, heat resistance is often lower than when a pigment is used.
Under such a background, as a dye-containing coloring composition capable of forming a pixel having excellent heat resistance, for example, patent document 5 proposes the use of a triarylmethane-based dye having an alkylsulfonylimide anion.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2-144502
Patent document 2: japanese laid-open patent publication No. 3-53201
Patent document 3: japanese laid-open patent publication No. 6-35188
Patent document 4: japanese patent laid-open No. 2000-310706
Patent document 5: japanese patent laid-open publication No. 2012-83652
Disclosure of Invention
However, the heat resistance of the dye of patent document 5 is not sufficient in practical cases. Accordingly, an object of the present invention is to provide a coloring composition suitable for forming a colored cured film exhibiting excellent heat resistance. Another object of the present invention is to provide a colored cured film formed using the colored composition, and a display device including the colored cured film.
As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using a compound having a specific structure together with a colorant.
That is, the present invention provides a coloring composition comprising (A) a coloring agent, (B) a polymerizable compound, and further comprising (C)2)1 or more kinds of polymers having a structural unit represented by the following formula (2), (3), (4) or (5).
In the formulas (2) to (5),
R1、R11、R21and R31Each independently represents a methyl group, a trifluoromethyl group or a hydrogen atom,
R12and R13Each independently represents a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group,
Rfrepresents a hydrogen atom, a halogen group, or a substituted or unsubstitutedAt least one RfIs a fluorine atom or an alkyl group having a fluorine atom,
y represents a 2-valent group or a single bond,
d represents a 2-valent organic group,
w represents a halogen group, a halogenated hydrocarbon group, or a 1-valent group having a linking group containing an atom other than a carbon atom, a hydrogen atom, or a halogen atom between C-C bonds of the halogenated hydrocarbon group,
a represents a 2-valent group or a single bond,
g represents a 2-valent organic group containing a fluorine atom or a single bond,
ar represents a substituted arylene group having at least 1 or more halogen groups,
e represents a 2-valent group or a single bond,
Xm+represents a proton,A cation or a metal ion, and a metal ion,
m represents a natural number of 1 to 3,
n represents an integer of 0 to 3,
p represents an integer of 1 to 8. Angle (c)
The present invention also provides a coloring composition comprising (A) a coloring agent, (B) a polymerizable compound, and (C)1) A compound represented by the following formula (1) and (D) a binder resin.
X+(ZaR0 bM)-(1)
In the formula (1), the following reaction conditions are satisfied,
X+represents a proton,A cation or an alkali metal ion, and a salt thereof,
z represents an electron-withdrawing group,
R0represents an alkyl, aryl, cycloalkyl or alkylaryl group,
m represents a nitrogen atom, a phosphorus atom, a boron atom, an arsenic atom or an antimony atom,
a represents an integer of 1 to 6,
b represents an integer of 0 to 5.
Wherein a + b is 2,4 or 6, Z, R0When a plurality of the compounds are present, they may be the same or different. Angle (c)
The present invention also provides a colored cured film formed using the colored composition and a display device including the colored cured film. Here, the "colored cured film" refers to pixels of each color, a black matrix, a black spacer, and the like used in a display element and a solid-state imaging element.
When the coloring composition of the present invention is used, a colored cured film exhibiting excellent heat resistance can be formed. In particular, when a dye is used as the colorant, a colored cured film exhibiting particularly excellent heat resistance can be formed.
Therefore, the coloring composition of the present invention is extremely suitable for producing color liquid crystal display elements, organic EL display elements, display elements such as electronic paper, and solid-state imaging elements such as CMOS image sensors.
Detailed Description
The present invention will be described in detail below.
Coloring composition
The constituent components of the coloring composition of the present invention will be described in detail below.
- (A) coloring agent-
The coloring agent is not particularly limited as long as it has coloring properties, and the color and material can be appropriately selected according to the use of the coloring composition. For example, when the colored composition of the present invention is used for forming a colored cured film of a color filter, since the color filter is required to have high color purity, brightness, contrast, and the like, at least 1 kind selected from pigments and dyes is preferable as the colorant, and at least 1 kind selected from organic pigments and organic dyes is particularly preferable. Among them, the organic dye is preferable because the desired effect of the present invention can be easily obtained.
As the dye, an acid dye, a basic dye and a nonionic dye can be preferably used. These may be used in 1 kind or in combination of 2 or more kinds, and when 2 or more kinds are used in combination, they may be arbitrarily combined. Here, the "acid dye" in the present specification means an ionic dye having an anionic portion as a chromophore, and an ionic dye having a salt with the anionic portion is also used as an acid dye. In the present specification, the term "basic dye" refers to an ionic dye in which a cationic moiety is a chromophore, and an ionic dye in which a salt is formed with the cationic moiety is also used as a basic dye. "nonionic dye" refers to dyes other than acid dyes and basic dyes.
Among the dyes, basic dyes are preferable from the viewpoint of further improving heat resistance. The basic dye is an ionic dye having a chromophore as a cationic portion, and is not particularly limited as long as it has a cationic chromophore, and examples thereof include azo-based basic dyes, triarylmethane-based basic dyes, xanthene-based basic dyes, quinoneimine-based basic dyes, and cyanine-based basic dyes. These may be used in 1 kind or in combination of 2 or more kinds, and when 2 or more kinds are used in combination, they may be arbitrarily combined. Among them, triarylmethane-based basic dyes and xanthene-based basic dyes are preferable.
The triarylmethane-based basic dye preferably has a cationic chromophore represented by the following formula (6-1) or (6-2). Although various resonance structures exist in the cationic chromophores represented by the following formulae (6-1) and (6-2), the present specification is the same as the chromophores represented by the formulae (6-1) and (6-2) when resonance structures exist in the chromophores represented by the respective formulae.
In the formulas (6-1) and (6-2),
R51～R56and R61～R66Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, or a substituted or unsubstituted aryl group,
R57～R59and R67～R69Each independently represents an alkyl group having 1 to 8 carbon atoms or a chlorine atom,
c. d, f, g and h each independently represent an integer of 0 to 4,
e represents an integer of 0 to 6. Angle (c)
R51～R59And R61～R69Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, a tert-pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a tert-octyl group, and a 2-ethylhexyl group. Among them, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is particularly preferable.
In the present specification, an alkyl group may be linear or branched.
As R51～R56And R61～R66Examples of the cycloalkyl group having 3 to 8 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Among them, a cycloalkyl group having 4 to 6 carbon atoms is preferable, and a cyclohexyl group is particularly preferable.
As R51～R56And R61～R66The aryl group preferably has 6 to 1 carbon atoms4. More preferably an aryl group having 6 to 10 carbon atoms. Specific examples thereof include phenyl, naphthyl and anthracenyl, and among them, phenyl is preferable.
As R51～R56And R61～R66Examples of the substituent for the alkyl group, the cycloalkyl group and the aryl group in (1) include an alkoxy group having 1 to 6 carbon atoms, a halogen group, a trifluoromethyl group, a cyano group and the like, and the cycloalkyl group and the aryl group may be substituted with an alkyl group having 1 to 6 carbon atoms. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a tert-butoxy group, a sec-butoxy group, a n-pentoxy group, an isopentoxy group, a n-hexoxy group, a methoxymethoxy group, an ethoxyethoxy group, and a 3- (isopropoxy) propoxy group. The alkoxy group in the present specification may be linear or branched. Examples of the halogen group include a fluoro group, a chloro group, a bromo group, and an iodo group. Specific examples of the alkyl group having 1 to 6 carbon atoms include the same groups as described above. The position and number of the substituents are arbitrary, and when 2 or more substituents are present, the substituents may be the same or different.
As R57～R59And R67～R69The alkyl group has preferably 1 to 4 carbon atoms or a chlorine atom, more preferably 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.
In the formula (6-1), c and d are preferably integers of 0 to 2, and e is preferably 0 or 1. The combination of c, d, and e is preferably a combination of c, d, and e, 0, and e, a combination of c, d, and e, 0, a combination of c, d, and e, a combination of c, d, and 1, and e, 1, and more preferably a combination of c, d, and 0, and e, a combination of c, d, and e, 0, and a combination of c, d, and e, and a combination of c, d, 0, and e, and a combination of c, d, and 1, d, and e, and 0.
In the formula (6-2), f is preferably an integer of 0 to 2, and g and h are preferably 0 or 1. Among these, as the combination of f, g, and h, a combination of f-0, g-0, and h-0, a combination of f-1, g-0, and h-0, a combination of f-2, g-0, and h-0, a combination of f-1, g-1, and h-1 is preferable, and a combination of f-1, g-0, and h-0, and a combination of f-1, g-1, and h-0 is particularly preferable.
Examples of the chromophore represented by the formula (6-1) or the chromophore represented by the formula (6-2) include chromophores represented by the following compound group a and compound group b, and among these chromophores, chromophores a1, a2, a3, a4, a5, a6, b1, b2, b3, b4, and b6 are preferable, and chromophores a3, a4, a5, a6, b3, and b4 are more preferable.
In addition to the above, examples of the cationic chromophore represented by the formula (6-1) include chromophores described in Japanese patent laid-open No. 2012-17425.
Examples of azo dyes include compounds having a cationic chromophore described in paragraphs [ 0066 ] to [ 0067 ] of Japanese patent laid-open Nos. 2012-108469.
The xanthene-based basic dye is preferably a cationic chromophore represented by the following formula (8).
In the formula (8), the following formula (C),
R101、R102、R103and R104Each independently represents a hydrogen atom, -R108Or an aromatic hydrocarbon group having 6 to 10 carbon atoms (wherein the aromatic hydrocarbon group may be a halogen group, -R108、-OH、-OR108、-SO3H、-SO3M1、-CO2H、-CO2R108、-SO3R108、-SO2NHR109or-SO2NR109R110Substituted);
R105and R106Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms;
R107represents-SO3H、-SO3M1、-CO2H、-CO2R108、-SO3R108、-SO2NHR109or-SO2NR109R110；
K represents an integer of 0 to 5, and when K is an integer of 2 or more, a plurality of R107May be the same or different;
R108represents a saturated hydrocarbon group having 1 to 10 carbon atoms (wherein the saturated hydrocarbon group may be substituted with a halogen group, and an oxygen atom, a carbonyl group or-NR may be present between C and C bonds of the saturated hydrocarbon group108-)；
R109And R110Each independently represents a chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms or-L, or R109And R110And a substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms bonded to each other. Wherein the alkyl and cycloalkyl groups may be substituted by hydroxy, halo, -L, -CH ═ CH2or-CH ═ CHR108Substituted, in addition, with oxygen atoms, carbonyl groups or-NR groups between the alkyl and the C-C bond of the cycloalkyl radical108-, the hydrogen atom contained in the heterocyclic group may be replaced by-R108-OH or-L;
M1represents a sodium atom or a potassium atom;
l represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms. Wherein the hydrogen atom contained in the aromatic hydrocarbon group and aromatic heterocyclic groupThe substituent may be substituted by-OH, -R108、-OR108、-NO2、-CH＝CH2、-CH＝CHR108Or a halogen group. Angle (c)
If R is108The saturated hydrocarbon group may have any of a straight chain, a branched chain and a cyclic structure, and may have a bridged structure, when the number of carbon atoms is 1 to 10. Examples of the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 3 to 8 carbon atoms include nonyl, decyl, tricyclodecyl, norbornyl, bornyl, adamantyl, and bicyclooctyl. Examples of the group having an oxygen atom between the C-C bonds of the saturated hydrocarbon group include a methoxypropyl group, an ethoxypropyl group, a 2-ethylhexyloxypropyl group, and a methoxyhexyl group.
As R109And R110Examples of the substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms which are bonded to each other include pyrrolidinyl, pyrazolinyl, morpholinyl, thiomorpholinyl, piperidinyl, piperidino, piperazinyl, homopiperazinyl, tetrahydropyrimidinyl, 1, 3-dioxolan-2-yl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, benzothiazolyl, and the like,Oxazolyl, indolyl, indazolyl, benzimidazolyl, phthalimidyl and the like. Examples of the substituent in the heterocyclic group include a halogen group, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an amino group, an alkyl group having 1 to 8 carbon atoms, and the like.
Examples of the aromatic heterocyclic group having 5 to 10 carbon atoms as L include furyl, thienyl, pyridyl, pyrrolyl, and the like,Azolyl radical, isoOxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, pyrimidinyl, and the like.
As R101、R102、R103、R104Examples of the aromatic hydrocarbon group in L include a phenyl group and a naphthyl group.
As R101、R102、R103、R104And R107In (C-SO)3R108Examples thereof include methanesulfonyl group, ethanesulfonyl group, hexanesulfonyl group, and decanesulfonyl group. In addition, as-CO2R108Examples thereof include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, cyclohexyloxycarbonyl and methoxypropyloxycarbonyl. In addition, as-SO2NHR109、-SO2NR109R110R in (1)109、R110Preferably, the alkyl group is a branched alkyl group having 6 to 8 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an allyl group, an aralkyl group having 8 to 10 carbon atoms, an alkyl group having 2 to 8 carbon atoms and containing a hydroxyl group, an alkyl group having 2 to 8 carbon atoms and containing an alkoxy group, and an aryl group having 6 to 10 carbon atoms.
Examples of the quinoneimine-based basic dye include compounds having a cationic chromophore described in paragraph [ 0078 ] of japanese patent application laid-open No. 2012-108469.
Examples of the cyanine-based basic dye include compounds having a cationic chromophore described in paragraphs [ 0064 ] to [ 0065 ] of Japanese patent laid-open No. 2012-212089.
Examples of the anion capable of forming a salt with the cationic chromophore include a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, and a methide anion.
Examples of the halogen ion include a fluoride ion, a chloride ion, a bromide ion, and an iodide ion.
Examples of the boron anion include BF4 -And inorganic boron anions;
(CF3)4B-、(CF3)3BF-、(CF3)2BF2 -、(CF3)BF3 -、(C2F5)4B-、(C2F5)3BF-、(C2F5)BF3 -、(C2F5)2BF2 -、(CF3)(C2F5)2BF-、(C6F5)4B-、[(CF3)2C6H3]4B-、(CF3C6H4)4B-、(C6F5)2BF2 -、(C6F5)BF3 -、(C6H3F2)4B-、B(CN)4 -、B(CN)F3 -、B(CN)2F2 -、B(CN)3F-、(CF3)3B(CN)-、(CF3)2B(CN)2 -、(C2F5)3B(CN)-、(C2F5)2B(CN)2 -、(n-C3F7)3B(CN)-、(n-C4F9)3B(CN)-、(n-C4F9)2B(CN)2 -、(n-C6F13)3B(CN)-、(CHF2)3B(CN)-、(CHF2)2B(CN)2 -、(CH2CF3)3B(CN)-、(CH2CF3)2B(CN)2 -、(CH2C2F5)3B(CN)-、(CH2C2F5)2B(CN)2 -、(CH2CH2C3F7)2B(CN)2 -、(n-C3F7CH2)2B(CN)2 -、(C6H5)3B(CN)-tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetrakis (tolyl) borate, tetraxylyl borate, (triphenyl, pentafluorophenyl) borate, [ tris (pentafluorophenyl) phenyl borate]Organic boron anions such as borate, tridecyl-7, 8-dicarbaundecaborate (tridehydrocide-7, 8-dicarbaundecabrate), and boron anions described in Japanese patent application laid-open Nos. H10-195119, 2010-094807, 2006-243594, 2002-341533, and 8-015521.
Examples of the phosphate anion include HPO4 2-、PO4 3-、PF6 -Inorganic phosphate anions;
(C2F5)2PF4 -、(C2F5)3PF3 -、[(CF3)2CF]2PF4 -、[(CF3)2CF]3PF3、(n-C3F7)2PF4 -、(n-C3F7)3PF3 -、(n-C4F9)3PF3 -、(C2F5)(CF3)2PF3 -、[(CF3)2CFCF2]2PF4 -、[(CF3)2CFCF2]3PF3 -、(n-C4F9)2PF4 -、(n-C4F9)3PF3 -、(C2F4H)(CF3)2PF3 -、(C2F3H2)3PF3 -、(C2F5)(CF3)2PF3 -organic phosphate anions such as octyl phosphate anion, dodecyl phosphate anion, octadecyl phosphate anion, phenyl phosphate anion, and nonyl phenyl phosphate anion.
Examples of the carboxylate anion include CH3COO-、C2H5COO-、C6H5COO-And carboxylate anions described in Japanese patent laid-open Nos. 2009-265641 and 2008-096680.
Examples of the sulfate anion include a sulfate anion and a sulfite anion.
Examples of the organic sulfonate anion include alkyl sulfonate anions such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, and nonafluorobutanesulfonic acid;
arylsulfonate anions such as benzenesulfonic acid, benzenedisulfonate ion, p-toluenesulfonic acid, p-trifluoromethylsulfonic acid, pentafluorobenzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonate ion, and organosulfonate anions described in pamphlet of International publication No. 2011/037195, Japanese patent No. 3736221, Japanese patent application laid-open No. 2011-.
Examples of the nitrogen anion include [ (CN)2N]-、[(FSO2)2N]-、[(FSO2)N(CF3SO2)]-、[(FSO2)N(CF3CF2SO2)]-、[(FSO2)N{(CF3)2CFSO2}]-、[(FSO2)N(CF3CF2CF2SO2)]-、[(FSO2)N(CF3CF2CF2CF2SO2)]-、[(FSO2)N{(CF3)2CFCF2SO2}]-、[(FSO2)N{CF3CF2(CF3)CFSO2}]-、[(FSO2)N{(CF3)3CSO2}]-And the nitrogen anions described in Japanese patent application laid-open Nos. 2011-133844, 2011-116803 and 2010-090341.
Examples of the methide anion include (CF)3SO2)3C-、(CF3CF2SO2)3C-、[(CF3)2CFSO2]3C-、(CF3CF2CF2SO2)3C-、(CF3CF2CF2CF2SO2)3C-、[(CF3)2CFCF2SO2]3C-、[CF3CF2(CF3)CFSO2]3C-、[(CF3)3CSO2]3C-、(FSO2)3C-And methide anions described in, for example, Japanese patent application laid-open Nos. 2011-145540, 5,554,664, 2005-309408, 2004-085657, and 2010-505787.
Examples of the acid dye include acid dyes described in japanese patent application laid-open nos. 2010-191358, 2011-138094, 2011-174987, 2012-008421 and 2012-013757.
Examples of The organic pigment include compounds classified as pigments in The color index (C.I.; issued by The Society of Dyersand Colourists Co.), among which lake pigments described in Japanese patent laid-open Nos. 2001-081348, 2010-026334, 2010-191304, 2010-237384, 2010-237569, 2011-006602, 2011-145346, C.I. pigment Red 166, C.I. pigment Red 177, C.I. pigment Red 224, C.I. pigment Red 242, C.I. pigment Red 254, C.I. pigment Red 264, C.I. pigment Green 7, C.I. pigment Green 36, C.I. pigment Green 58, C.I. pigment blue 15: 6. organic pigments other than lake pigments such as c.i. pigment blue 80, c.i. pigment yellow 83, c.i. pigment yellow 129, c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 150, c.i. pigment yellow 185, c.i. pigment yellow 211, c.i. pigment yellow 215, c.i. pigment orange 38, and c.i. pigment violet 23. Among the lake pigments, triarylmethane lake pigments, xanthene lake pigments and azo lake pigments are preferable, and triarylmethane lake pigments and xanthene lake pigments are more preferable. These organic pigments can be suitably used according to the color tone of the coloring composition.
In the present invention, the pigment may be purified by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof. These pigments may be used by modifying the particle surface with a resin as necessary. Examples of the resin for modifying the particle surface of the pigment include a vehicle resin (ビヒクル resin) described in japanese patent application laid-open No. 2001-108817, and various commercially available resins for dispersing the pigment. As a method for coating the surface of carbon black with a resin, for example, the methods described in Japanese patent application laid-open Nos. 9-71733, 9-95625, and 9-124969 are used. The organic pigment can be used by making primary particles fine by so-called salt milling. As a method of salt milling, for example, the method disclosed in Japanese patent application laid-open No. 8-179111 can be used.
In the present invention, at least 1 kind selected from known dispersants and dispersing aids may be further contained in addition to the pigment. Examples of the known dispersant include a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene alkylphenyl ether-based dispersant, a polyethylene glycol diester-based dispersant, a sorbitan fatty acid ester-based dispersant, a polyester-based dispersant, and an acrylic dispersant, and examples of the dispersing aid include a pigment derivative.
Such a dispersant is commercially available, and examples of the acrylic dispersant include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (BYK-Chemie (BYK), the urethane dispersants include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (BYK-Chemie (BYK)), Solsperse76500(Lubrizol corporation), the polyethyleneimine dispersants include Solsperse24000(Lubrizol corporation), the polyester dispersants include Adisper PB, Adisper 822, Adisper 880, Adsperse 24000 (ByK-Chemie corporation), the BYK-21324, and BYK-Chi), the polyester dispersants include BYK-2000 (BYK-Chemie corporation).
Specific examples of the pigment derivative include sulfonic acid derivatives of copper phthalocyanine, diketopyrrolopyrrole, quinophthalone, and the like.
In the present invention, the pigments may be used alone or in combination of 2 or more.
The content of the colorant (a) is usually 5 to 70% by mass, preferably 5 to 60% by mass in the solid content of the coloring composition, from the viewpoint of forming a pixel having high heat resistance and brightness and excellent color purity, or a black matrix or a black spacer having excellent light-shielding properties. The solid component herein is a component other than the solvent described later.
(B) polymerizable compound-
In the present invention, the polymerizable compound means a compound having 2 or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an epoxyethyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, as the polymerizable compound, a compound having 2 or more (meth) acryloyl groups or a compound having 2 or more N-alkoxymethylamino groups is preferable.
Specific examples of the compound having 2 or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, a polyfunctional (meth) acrylate modified with caprolactone, a polyfunctional (meth) acrylate modified with an alkylene oxide, a polyfunctional urethane (meth) acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, and a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride.
Here, examples of the aliphatic polyhydroxy compound include 2-valent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; aliphatic polyhydric compounds having a valence of 3 or more such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol. Examples of the (meth) acrylate having the 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. Examples of the acid anhydride include dicarboxylic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride and hexahydrophthalic anhydride, and tetracarboxylic acid dianhydrides such as pyromellitic dianhydride, biphenyltetracarboxylic acid dianhydride and benzophenonetetracarboxylic acid dianhydride.
Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in [ 0015 ] to [ 0018 ] of Japanese patent laid-open No. 11-44955. Examples of the above-mentioned alkylene oxide-modified polyfunctional (meth) acrylate include bisphenol A di (meth) acrylate modified with at least 1 kind selected from ethylene oxide and propylene oxide, isocyanuric acid tri (meth) acrylate modified with at least 1 kind selected from ethylene oxide and propylene oxide, trimethylolpropane tri (meth) acrylate modified with at least 1 kind selected from ethylene oxide and propylene oxide, pentaerythritol tri (meth) acrylate modified with at least 1 kind selected from ethylene oxide and propylene oxide, pentaerythritol tetra (meth) acrylate modified with at least 1 selected from ethylene oxide and propylene oxide, dipentaerythritol penta (meth) acrylate modified with at least 1 selected from ethylene oxide and propylene oxide, dipentaerythritol hexa (meth) acrylate modified with at least 1 selected from ethylene oxide and propylene oxide, and the like.
Examples of the compound having 2 or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and benzoguanamine structure are chemical structures having 1 or more triazine rings or phenyl-substituted triazine rings as basic skeletons, and are concepts including melamine, benzoguanamine, and condensates thereof. Specific examples of the compound having 2 or more N-alkoxymethylamino groups include N, N ', N ", N ″ -hexa (alkoxymethyl) melamine, N ' -tetrakis (alkoxymethyl) benzoguanamine, N ' -tetrakis (alkoxymethyl) glycoluril, and the like.
Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting (meth) acrylic acid with an aliphatic polyhydric compound having a valence of 3 or more, polyfunctional (meth) acrylates modified with caprolactone, polyfunctional urethane (meth) acrylates, polyfunctional (meth) acrylates having a carboxyl group, N ', N ", N ″ -hexa (alkoxymethyl) melamine, and N, N' -tetrakis (alkoxymethyl) benzoguanamine are preferable. Among polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydric compound having a valence of 3 or more with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferable, and among polyfunctional (meth) acrylates having a carboxyl group, compounds obtained by reacting pentaerythritol triacrylate with succinic anhydride, and compounds obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride are particularly preferable, from the viewpoint that the colored layer has high strength, the colored layer has excellent surface smoothness, and unexposed portions are less likely to cause dirt, film residue, and the like on the substrate and the light-shielding layer.
In the present invention, the polymerizable compound (B) may be used alone or in combination of 2 or more.
The content of the polymerizable compound (B) in the present invention is preferably 10 to 1000 parts by mass, more preferably 20 to 700 parts by mass, and still more preferably 100 to 600 parts by mass, based on 100 parts by mass of the colorant (A). In this manner, the curability and the alkali developability can be further improved, and the occurrence of dirt, film residue, and the like on the substrate or the light-shielding layer at the unexposed portion can be suppressed at a high level.
- (C) specific compound-
The coloring composition of the present invention contains (C)1) Component (A) or (C)2) Component (C) is a specific compound. In the following description, (C) may be used1) And (C)2) Components are collectively described as "(C) a specific compound".
The specific compound (C) in the present invention is a compound having a maximum value of molar absorption coefficient in the visible light region (380nm to 780nm) of 10000 or less, and the maximum value of molar absorption coefficient in the visible light region is preferably 5000 or less, and more preferably 3000 or less.
First, pair (C)1) Component (A) and (B)2) The anion part of the component (A) will be described.
(C1) Component (A) having an anion moiety of (Z)aR0 bM)-And (4) showing.
Z is not particularly limited as long as it is an electron-withdrawing group, and examples thereof include a halogen group, a 1-valent organic group having a halogen group, a cyano group, a 1-valent organic group having a nitro group, a halosulfonyl group, an alkylsulfonyl group which may have a halogen group, and the like.
Examples of the halogen group include the same groups as described above, and among them, a fluorine group is preferable from the viewpoint of heat resistance.
The 1-valent organic group having a halogen group is not particularly limited, and examples thereof include a 1-valent halogenated hydrocarbon group which may have a substituent other than a halogen group. The hydrocarbyl group serving as a skeleton of the halogenated hydrocarbyl group is preferably an alkyl group, a cycloalkyl group, an aryl group, or an alkylaryl group, and more preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 8 carbon atoms, the cycloalkyl group having 3 to 8 carbon atoms and the aryl group having 6 to 14 carbon atoms include the same groups as described above. Examples of the alkylaryl group include those wherein the alkyl group having 1 to 8 carbon atoms is substituted with an aryl group having 6 to 14 carbon atoms.
As the halogen group in the halogenated hydrocarbon group, a fluorine group is preferable. The halogen group may be substituted for part or all of the hydrogen atoms of the hydrocarbon group, and in particular, the hydrogen atoms of the hydrocarbon group are preferably substituted by 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 100 mol% with the halogen group. This can further improve heat resistance.
The 1-valent organic group having a cyano group is not particularly limited, and examples thereof include a 1-valent hydrocarbon group substituted with a cyano group, and the 1-valent hydrocarbon group may have a substituent other than a cyano group. As the 1-valent hydrocarbon group, an aryl group is preferable, and a phenyl group is particularly preferable.
The 1-valent organic group having a nitro group is not particularly limited, and examples thereof include a 1-valent hydrocarbon group substituted with a nitro group, and the 1-valent hydrocarbon group may have a substituent other than a nitro group. As the 1-valent hydrocarbon group, an aryl group is preferable, and a phenyl group is particularly preferable.
The alkylsulfonyl group which may have a halogen group is not particularly limited, and an alkylsulfonyl group or a haloalkylsulfonyl group may be appropriately selected and used. The number of carbon atoms of the alkyl group constituting the skeleton of the alkylsulfonyl group and the haloalkylsulfonyl group is preferably 1 to 8. Specific examples of the alkyl group include the same groups as described above. Further, as the halogen group in the haloalkylsulfonyl group, a fluoro group is preferable. The halogen group may be substituted for a part or all of the hydrogen atoms of the hydrocarbon group, and from the viewpoint of heat resistance, 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 100 mol% of the hydrogen atoms of the hydrocarbon group are substituted with the halogen group.
As the halosulfonyl group, FSO is mentioned2Basic group, ClSO2Basic group, BrSO2Base, ISO2Preferably FSO2And (4) a base.
When M is a phosphorus atom, a boron atom, an arsenic atom or an antimony atom, Z is preferably a halogen group, a 1-valent halogenated hydrocarbon group which may have a substituent other than a halogen group, or a cyano group, and particularly preferably a fluoro group, a cyano group, a fluoroalkyl group, a fluoroaryl group or a fluoroalkylaryl group. The fluoroalkyl group is preferably a perfluoroalkyl group, and the perfluoroalkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. Specific examples thereof include CF3Basic, CF3CF2Radical, (CF)3)2CF group, CF3CF2CF2Basic, CF3CF2CF2CF2Radical, (CF)3)2CFCF2Basic, CF3CF2(CF3) CF group, (CF)3)3C group, etc. The fluorinated aryl group is preferably a perfluoroaryl group, and the number of carbon atoms of the perfluoroaryl group is preferably 6 to 14, more preferably 6 to 10. Specific examples thereof include a pentafluorophenyl group and the like. The fluoroalkylaryl group is preferably a perfluoroalkylaryl group, and the number of carbon atoms in the perfluoroalkylaryl group is preferably 7 to 20, more preferably 7 to 16. Specific examples thereof include CF3Phenyl substituted with phenyl, and the like.
On the other hand, when M is a nitrogen atom, Z is preferably a cyano group, a halosulfonyl group or a halo groupAlkylsulfonyl, particularly preferably fluoroalkylsulfonyl. Specific examples of the fluoroalkylsulfonyl group include CF3SO2Basic, CF3CF2SO2Radical, (CF)3)2CFSO2Basic, CF3CF2CF2SO2Basic, CF3CF2CF2CF2SO2Radical, (CF)3)2CFCF2SO2Basic, CF3CF2(CF3)CFSO2Radical, (CF)3)3CSO2And the like.
R0The alkyl, aryl, cycloalkyl or alkylaryl group is preferably an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or an alkylaryl group having 7 to 20 carbon atoms. Specific examples thereof include the same groups as described above.
Among nitrogen atoms, phosphorus atoms, boron atoms, arsenic atoms, and antimony atoms, M is preferably a nitrogen atom, a phosphorus atom, or a boron atom from the viewpoint of safety.
Note that a + b represents 2,4, or 6, and when M is a nitrogen atom, a + b is 2, when M is a boron atom, a + b is 4, and when M is a phosphorus atom, an arsenic atom, or an antimony atom, a + b is 6. Incidentally, Z and R0When a plurality of the compounds are present, they may be the same or different.
a represents an integer of 1 to 6, b represents an integer of 0 to 5, and in the present invention, b is preferably 0, that is, a is 2,4 or 6.
In the present invention, (Z) is preferableaR0 bM)-Examples thereof include anions represented by any of the following formulae (1a) to (1 c).
[(R1a)lP Hal6-l]-(1a)
[ in the formula (1a), R1aRepresents a halogenated hydrocarbon group, P represents a phosphorus atom, Hal represents a halogen group, and l represents an integer of 0 to 6. R1aAnd Hal may be the same or different when a plurality of Hal are present. Angle (c)
[(R1b)qB Hal4-q]-(1b)
[ in the formula (1b), R1bEach independently represents a halogenated hydrocarbon group, a cyano group, or a phenyl group substituted with a nitro group or a cyano group, B represents a boron atom, Hal represents a halogen group, and q represents an integer of 0 to 4. R1bAnd Hal may be the same or different when a plurality of Hal are present. Angle (c)
[(EA)2N]-(1c)
In the formula (1c), EA represents cyano group and FSO independently of each other2Or a fluoroalkylsulfonyl group. Wherein at least one of the 2 EA's represents a cyano group or FSO2And (4) a base. Angle (c)
R1aThe halogenated hydrocarbon group includes the halogenated hydrocarbon groups listed in the description of Z. In the present invention, R1aThe fluoroalkyl group is preferable, and more specifically, the fluoroalkyl groups listed in the description of Z are preferable.
R1bEach independently represents a halogenated hydrocarbon group, a cyano group, or a phenyl group substituted with a nitro group or a cyano group, and examples of the halogenated hydrocarbon group include the halogenated hydrocarbon groups exemplified in the description of Z above. In the present invention, R1bPreferred is a fluoroalkyl group, a fluoroaryl group, a cyano group, or a phenyl group substituted with a trifluoromethyl group or a fluorine atom, and more specifically, preferred is a group exemplified in the description of Z above.
Hal in the formulae (1a) and (1b) is preferably a fluoro group from the viewpoint of heat resistance.
EA of formula (1c) represents cyano group, FSO2Or a fluoroalkylsulfonyl group. As the fluoroalkylsulfonyl group, the fluoroalkylsulfonyl groups exemplified in the description of Z above are preferred. In the formula (1c), EA is preferably 2 groups each of cyano group or FSO2Radical, or one is FSO2Radical and the other is fluoroalkylA sulfonyl group.
Typical examples of the anion represented by the formula (1a) include the same anions as those exemplified in the above paragraph [ 0041 ]. Among them, PF is preferred6 -、(C2F5)2PF4 -、(C2F5)3PF3 -、(n-C3F7)3PF3 -、(n-C4F9)3PF3 -、[(CF3)2CF]3PF3 -、[(CF3)2CF]2PF4 -、[(CF3)2CFCF2]3PF3 -、[(CF3)2CFCF2]2PF4 -。
Typical examples of the anion represented by the formula (1b) include the same anions as those exemplified in the above paragraph [ 0040 ]. Among them, BF is preferred4 -、B(CN)3F-、B(CN)4 -、(CF3)4B-、(C6F5)4B-、[(CF3)2C6H3]4B-。
Among the anions represented by the formula (1c), preferable examples of the anion include the same anions as those exemplified in the above paragraph [ 0044 ]. Among them, preferred is [ (CN)2N]-。
In addition, (C)2) The anion portion relating to the component (a) is a structural unit represented by any one of the following formulae (2 ') to (5').
In the formulas (2 ') to (5'),
R1、R11、R21and R31Each independently represents a methyl group, a trifluoromethyl group or a hydrogen atom,
R12and R13Each independently represents a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group,
Rfrepresents a hydrogen atom, a halogen group, or a substituted or unsubstituted hydrocarbon group, at least one RfIs a fluorine atom or an alkyl group having a fluorine atom,
y represents a 2-valent group or a single bond,
d represents a 2-valent organic group,
w represents a halogen group, a halogenated hydrocarbon group, or a 1-valent group having a linking group containing an atom other than a carbon atom, a hydrogen atom, or a halogen atom between C-C bonds of the halogenated hydrocarbon group,
a represents a 2-valent group or a single bond,
g represents a 2-valent organic group containing a fluorine atom or a single bond,
ar represents a substituted arylene group having at least 1 or more halogen groups,
e represents a 2-valent group or a single bond,
m represents a natural number of 1 to 3,
n represents an integer of 0 to 3,
p represents an integer of 1 to 8. Angle (c)
In the methyl, trifluoromethyl and hydrogen atom, R1、R11、R21And R31Preferably a hydrogen atom or a methyl group, more preferably a methyl group.
The halogen group referred to for W is preferably a fluoro group.
The hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group represented by W is preferably an aliphatic hydrocarbon group, an alicyclic hydrocarbon-substituted aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon-substituted aromatic hydrocarbon group, or an aromatic hydrocarbon-substituted aliphatic hydrocarbon group.
The aliphatic hydrocarbon group may be linear or branched, and the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and the unsaturated aliphatic hydrocarbon group may have an unsaturated bond in any of the molecule and the terminal. Among these, the aliphatic hydrocarbon group is preferably an alkyl group having preferably 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms. Specific examples of the alkyl group include the same groups as described above.
The alicyclic hydrocarbon group may be a2 to 4-ring bridged alicyclic hydrocarbon group. The alicyclic hydrocarbon group is preferably an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. Specific examples thereof include the same cycloalkyl groups and bridged alicyclic hydrocarbon groups as described above.
The alicyclic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an alicyclic saturated hydrocarbon-substituted alkyl group having preferably 4 to 20 carbon atoms, more preferably 6 to 14 carbon atoms. Specific examples thereof include cyclopropylmethyl group, cyclobutylmethyl group, cyclohexylmethyl group, cyclohexylpropyl group, adamantylmethyl group, 1- (1-adamantyl) ethyl group, cyclopentylethyl group and the like.
The aromatic hydrocarbon group is preferably an aryl group having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. Specific examples thereof include phenyl, naphthyl, biphenyl, fluorenyl, anthracenyl and the like, and among them, phenyl is preferable.
The aliphatic hydrocarbon-substituted aromatic hydrocarbon group is preferably an alkyl-substituted phenyl group, and the number of carbon atoms of the alkyl-substituted phenyl group is preferably 7 to 30, more preferably 7 to 20. Specific examples thereof include tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl and the like.
The aromatic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an aralkyl group, and the number of carbon atoms in the aralkyl group is preferably 7 to 30, more preferably 7 to 20. Specific examples thereof include benzyl, phenethyl, α -methylbenzyl, and 2-phenylpropan-2-yl.
Among these, the hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group represented by W is preferably an aliphatic hydrocarbon group, an alicyclic hydrocarbon-substituted aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon-substituted aromatic hydrocarbon group, an aromatic hydrocarbon-substituted aliphatic hydrocarbon group, more preferably an alkyl group, an alicyclic saturated hydrocarbon-substituted alkyl group, a phenyl group, an alkyl-substituted phenyl group, or an aralkyl group, and particularly preferably an alkyl group.
The halogen atom in the halogenated hydrocarbon group represented by W is preferably a fluorine atom which may be substituted for a part or all of the hydrogen atoms in the hydrocarbon group, from the viewpoint of the heat resistance of the colorant. It is considered that by selecting a fluorine atom as a substituent, a salt having a stronger ionic bonding force can be formed and the heat resistance can be improved.
Further, W may be a 1-valent group having a linking group containing an atom other than a carbon atom, a hydrogen atom, or a halogen atom between C-C bonds of the halogenated hydrocarbon groups. Examples of the linking group containing an atom other than carbon, hydrogen or halogen include-O-, -S-, -CO-, -COO-, -CONH-, -SO2-and the like. When the linking group has a carbon atom, the number of carbon atoms of the hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group means the total number of carbon atoms excluding the carbon atoms constituting the linking group.
In the present invention, W is preferably a halogenated hydrocarbon group or a group having a linking group containing an atom other than a carbon atom, a hydrogen atom or a halogen atom between C — C bonds of the halogenated hydrocarbon group, more preferably a group represented by the following formula (11) or (12), and particularly preferably a group represented by the following formula (11) which forms a conjugate base of an organic acid having a stronger acidity, from the viewpoint of heat resistance of the colorant.
In the formula (11), in the following formula,
R40represents a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, an alicyclic hydrocarbon group, an alkoxy group, a fluoroalkoxy group, R41COOR42-or R43COOR44CFH-，
R41And R43Each independently represents an alkyl group, an alicyclic hydrocarbon group, or a substituted or unsubstituted aryl group,
R42and R44Each independently represents an alkanediyl group,
r represents an integer of 1 or more,
"Tuo" indicates a bonding site. Angle (c)
In the formula (12), in the following formula,
R45～R49each independently represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluoroalkyl group or an alkoxy group,
"Tuo" indicates a bonding site.
Wherein R is45～R49At least one of which is a fluorine atom or a fluoroalkyl group. Angle (c)
In the formula (11), R40The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specific examples thereof include the same groups as described above.
In addition, R40The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 4 carbon atoms. The fluoroalkyl group in the present specification may be a linear or branched one, and specific examples thereof include those in which some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and a perfluoroalkyl group is particularly preferable.
R40The alicyclic hydrocarbon group may be 2 to 4 ringsA bridged alicyclic hydrocarbon group. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 20, and more preferably 3 to 12. Specific examples thereof include the same groups as described above.
R40The alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and further preferably 1 to 4 carbon atoms. Specific examples thereof include the same groups as described above.
R40The number of carbon atoms of the fluoroalkoxy group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. Specific examples thereof include those wherein some or all of the hydrogen atoms of the above alkoxy group are replaced by fluorine atoms.
R40To R41COOR42-、R43COOR44In CFH-, R41And R43Each independently represents an alkyl group, an alicyclic hydrocarbon group, or a substituted or unsubstituted aryl group. The number of carbon atoms of the alkyl group is preferably 1 to 12, and more preferably 1 to 8. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 20, and more preferably 3 to 12. The number of carbon atoms of the aryl group is preferably 6 to 14, and more preferably 6 to 10. Specific examples thereof include the same groups as described above. Examples of the substituent for the aryl group include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen group, and a trifluoromethyl group. The number and position of the substituents are arbitrary, and when 2 or more substituents are present, the substituents may be the same or different.
Wherein, as R40Preferably a fluorine atom, a fluoroalkyl group, an alicyclic hydrocarbon group, a fluoroalkoxy group, R41COOR42-or R43COOR44CFH-, particularly preferably fluorine atom, alicyclic hydrocarbon group, perfluoroalkoxy group, R41COOCH2CH2-or R43COOCH2CH2CFH-。
R42And R44Each independently represents an alkanediyl group. The alkanediyl group may be linear or branched and has a high carbon numberIs selected from 1 to 10. Specific examples thereof include methylene, ethylene, ethane-1, 1-diyl, propane-1, 2-diyl, propane-1, 3-diyl, propane-2, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, octane-1, 8-diyl, decane-1, 10-diyl, and the like. Among them, an alkanediyl group having 2 to 6 carbon atoms is preferable, an alkanediyl group having 2 to 4 carbon atoms is more preferable, and an ethylene group is preferable from the viewpoint of ease of production.
The upper limit of r is preferably 10, and more preferably 8.
In the formula (12), R is45～R49As the alkyl, fluoroalkyl and alkoxy, the same groups as those mentioned above for R of the formula (11) can be used40The alkyl group, the fluoroalkyl group and the alkoxy group are the same. Wherein R is45～R49At least one of which is a fluorine atom or a fluoroalkyl group, preferably R45～R49At least 3 of which are fluorine atoms or fluoroalkyl groups.
Examples of the 2-valent organic group relating to D and G include a 2-valent hydrocarbon group, a group in which a 2-valent hydrocarbon group is combined with a linking group containing atoms other than carbon atoms and hydrogen atoms, or a group in which some of the hydrogen atoms of these groups are substituted with halogen atoms. Examples of the 2-valent hydrocarbon group include a 2-valent aliphatic hydrocarbon group, a 2-valent alicyclic hydrocarbon group, and a 2-valent aromatic hydrocarbon group. The 2-valent aliphatic hydrocarbon group may be either a straight chain or a branched chain, and the 2-valent aliphatic hydrocarbon group and the 2-valent alicyclic hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group.
Examples of the 2-valent aliphatic hydrocarbon group include an alkanediyl group and an alkenediyl group. The number of carbon atoms of the alkanediyl group is preferably 1 to 20, more preferably 2 to 12, and still more preferably 2 to 6. The number of carbon atoms of the alkenediyl group is preferably 2 to 20, more preferably 2 to 12, and still more preferably 2 to 6. Specific examples of the alkenediyl group include ethylene-1, 1-diyl, ethylene-1, 2-diyl, propylene-1, 3-diyl, propylene-2, 3-diyl, 1-butene-1, 2-diyl, 1-butene-1, 3-diyl, 1-butene-1, 4-diyl, 2-pentene-1, 5-diyl, and 3-hexene-1, 6-diyl. Specific examples of the alkanediyl group include the same groups as described above.
Examples of the 2-valent alicyclic hydrocarbon group include a cycloalkylene group and a cycloalkenylene group, and the number of carbon atoms thereof is preferably 3 to 20, and more preferably 3 to 12. Specific examples thereof include monocyclic hydrocarbon ring groups such as cyclopropylene, cyclobutylene, cyclopentylene, cyclobutenyl, cyclopentenylene and cyclohexenylene, norbornyl groups such as 1, 4-norbornylene and 2, 5-norbornylene, bridged hydrocarbon ring groups such as 1, 5-adamantylene and 2, 6-adamantylene, and the like.
The 2-valent aromatic hydrocarbon group includes, for example, an arylene group, and the number of carbon atoms thereof is preferably 6 to 20, and more preferably 6 to 10. Specific examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, and an anthracenyl group.
The 2-valent organic group may be an arylene alkandiyl group in which an arylene group and an alkandiyl group are combined. The number of carbon atoms of the arylene alkanediyl group is preferably 7 to 15, more preferably 7 to 13. Specific examples thereof include phenylene group C such as phenylene methylene, phenylene dimethylene, phenylene trimethylene, phenylene tetramethylene, phenylene pentamethylene, and phenylene hexamethylene1-6An alkanediyl group. In the arylene alkanediyl group, an adjacent body, a spacer and a para body are present, and the para body is preferable from the viewpoint of small steric hindrance.
Examples of the group in which a 2-valent hydrocarbon group is combined with a linking group containing atoms other than carbon atoms and hydrogen atoms include a combination of at least 1 selected from an alkanediyl group having 1 to 10 carbon atoms and/or an arylene group having 6 to 20 carbon atoms with a linking group selected from-O-, -S-, - (CO) O-, -O (CO) -, -CO-, -NR ' -, -CONR ' - (R ' represents an alkyl group having 1 to 8 carbon atoms which may have a hydrogen atom or a halogen atom), and-SO2A combination of at least 1 of (A) and (B), and the like.
G is a group substituted with a fluoro group among these 2-valent organic groups, and the position of substitution with a fluoro group is arbitrary, and a part or all of the organic groups may be substituted.
Among them, the alkanediyl group and the arylene group are preferable as D, and the alkanediyl group having a fluorine atom is preferable as G, and all of the alkanediyl groups are preferably substituted by a fluorine atom.
Y, A and E are each a 2-valent group containing a hetero atom in addition to the above 2-valent organic group. Examples of the 2-valent group containing a hetero atom include-O-, -S-, - (CO) O-, -O (CO) -, -CO-, -NR ' -, -CONR ' - (R ' represents an alkyl group having 1 to 8 carbon atoms and may have a hydrogen atom or a halogen atom), and-SO2-. The 2-valent organic group may have the same structure as described above.
Among these, Y, A, E is preferably a 2-valent group containing a hetero atom, and more preferably-O-, - (CO) O-, -CONH-.
As R12And R13The aliphatic hydrocarbon group may be a linear, branched or cyclic one, and the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and the unsaturated aliphatic hydrocarbon group may have an unsaturated bond in any of the intramolecular and terminal positions. Examples of the substituent of the aliphatic hydrocarbon group include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, and an amino group. Among these, the aliphatic hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 6 carbon atoms. Specific examples thereof include the same groups as described above.
As RfThe halogen group concerned is preferably a fluorine group.
In addition, as RfThe hydrocarbon group of the present invention may have the same structure as the hydrocarbon group of the W which is a skeleton of the halogenated hydrocarbon group, and is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 6 carbon atoms. Specific examples thereof includeThe same groups as described above.
Wherein, as RfPreferably, a fluorine group or a perfluoroalkyl group is used. Specific examples of the perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, an undecafluoropentyl group, a tridecafluorohexyl group, a pentadecafluoroheptyl group, a heptadecafluorooctyl group, a nonafluorononyl group, a heneicosanodecanyl group, (1-trifluoromethyl) tetrafluoroethyl group, (1-trifluoromethyl) hexafluoropropyl group, and 1, 1-bistrifluoromethyl-2, 2, 2-trifluoroethyl group.
The number of carbon atoms of the arylene group related to Ar is preferably 6 to 20, and more preferably 6 to 10. Specific examples of the arylene group include the same groups as described above. The halogen group may be substituted for a part or all of the arylene group, and as the halogen group, a fluorine group is preferable.
n represents an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1.
p represents an integer of 1 to 8, preferably an integer of 1 to 6, and more preferably an integer of 2 to 6.
(C2) The anion portion relating to the component (b) may have a structural unit (hereinafter, also referred to as "other structural unit") other than the structural units represented by the formulae (2 ') to (5'). Examples of such a structural unit include, for example, at least 1 monomer unit selected from the unsaturated monomer (D1) and the unsaturated monomer (D2) exemplified in the section (D) binder resin described later. Among these, from the viewpoint of dispersibility, the unsaturated monomer (d2) is preferably contained as a monomer unit, and the (meth) acrylate is more preferably contained as a monomer unit.
(C2) When the anionic portion of the component (b) has another structural unit, the copolymerization ratio of the other structural unit is preferably as follows from the viewpoint of dispersibility.
That is, (C)2) The ratio p of the structural units represented by the formulae (2 ') to (5') in the total structural units of the anion portion relating to the component (a) to the ratio r of the other structural units are preferably 5/95 to 50/50, more preferably 10/90 to 30 in terms of molar ratio/70。
(C2) The components were purified by gel permeation chromatography (hereinafter, abbreviated as GPC) (elution solvent: tetrahydrofuran) is usually 1000 to 50000, preferably 3000 to 20000 in terms of polystyrene-equivalent weight average molecular weight (Mw). In this manner, heat resistance, film properties, electrical properties, pattern shape, and resolution can be improved.
In addition, (C) in the present invention2) The ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the component (B) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. The Mn referred to herein is a number average molecular weight in terms of polystyrene as measured by GPC (elution solvent: tetrahydrofuran).
(C2) The component can be produced by a known method, for example, the same method as in the example of Japanese patent laid-open No. 2012-194466. The colorant thus obtained is soluble in various organic solvents represented by propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and the like, and has excellent heat resistance.
Then, pair (C)1) Component (A) and (B)2) The cation portion of the component (A) will be described.
Xm+Represents a proton,A cation or a metal ion. AsThe cation is preferably a cation having a maximum value of molar absorption coefficient in the visible light region (380nm to 780nm) of 10000 or less, preferably 5000 or less, and more preferably 3000 or less. Specifically, ammonium cations,Cation, sulfonium cation, iodineCation, diazoniumCations, and the like. The ammonium cation is preferably an organic ammonium cation, and examples thereof include tetramethylammonium, tetraethylammonium, monostearyltrimethylammonium, distearyldimethylammonium, tristearylmethylammonium, hexadecyltrimethylammonium, trioctylmethylammonium, dioctyldimethylammonium, monolauryltrimethylammonium, dilauryldimethylammonium, trilaurylmethylammonium, tripentylbenzylammonium, trihexylbenzylammonium, trioctylbenzylammonium, trilaurylbenzylammonium, benzyldimethylstearylammonium, benzyldimethyloctylammonium, and dialkyl (alkyl groups of C14 to C18) dimethylammonium. As mentioned aboveCationic, preferably organicExamples of the cation include methyltrioctyleneOctyl tributylDodecyl tributylHexadecyl tributylDihexyldioctyl groupAlkyl radicals of iso-tetraBenzyl tributyl radicalIso aryl trialkylDibutyl diphenyl groupIsodialkyldiarylButyl triphenyl phosphonium saltIsoalkyltriphenyleneBenzyl triphenylIso-tetra aryl radicalAnd the like. Examples of the sulfonium cation include those described in paragraph [ 0063 ] of Japanese patent laid-open No. 2009-073871. As the above iodineExamples of the cation include those described in paragraph [ 0065 ] of Japanese patent laid-open No. 2009-073871. As the above-mentioned diazoExamples of the cation include those described in paragraph [ 0374 ] of Japanese patent application laid-open No. 2002-332271.
Examples of the metal ion include a 1-valent metal cation such as a lithium ion, a sodium ion, and a potassium ion, and a 2-valent metal cation such as a magnesium ion and a calcium ion.
m represents a natural number of 1 to 3, and is appropriately selected so as to be electrically neutral with respect to the anionic portion, depending on the kind of the cationic chromophore described later.
In the present invention, (C) the specific compound may be used alone or in combination of 2 or more, but preferably contains at least (C) from the viewpoint of heat resistance and electric characteristics2) And (3) components. In (C)2) Among the components (a), preferred are polymers having a structural unit represented by the formula (2), (4) or (5), and more preferred are polymers having a structural unit represented by the formula (2) or (4).
In the present invention, (C) is used1) A compound represented by the above formula (1) or (C)2) In the case of any of the polymers having the structural units represented by the above formulae (2) to (5), the content of the specific compound (C) is preferably 10 to 500 parts by mass, more preferably 20 to 300 parts by mass, and still more preferably 30 to 200 parts by mass, based on 100 parts by mass of the colorant (A). Will (C)1) A compound represented by the above formula (1) and (C)2) When any of the polymers having the structural units represented by the above formulae (2) to (5) is used in combination, the total content thereof is preferably 10 to 500 parts by mass, more preferably 15 to 300 parts by mass, and still more preferably 20 to 200 parts by mass, based on 100 parts by mass of the colorant (a). In this manner, a colored cured film having high heat resistance can be obtained.
In particular, in the case of a coloring composition containing a dye as a colorant, the content of the specific compound (C) is preferably as follows.
Containing only (C)1) When the component (C) is the specific compound, the amount of the component (C) is 1 mol based on the dye1) The amount of the component (B) is preferably 1.0 to 10 mol, more preferably 1.5 to 8 mol, and still more preferably 2 to 7 mol.
Containing only (C)2) When the component (C) is the specific compound, the amount of the component (C) is 1 mol based on the dye2) The amount of the anion in the component (B) is preferably 1.0 to 10 mol, more preferably 1.5 to 8 mol, and still more preferably 2 to 7 mol.
In combination with (C)1) Component (A) and (B)2) When the component (C) is the specific compound, the amount of the component (C) is 1 mol based on the dye1) Component (A) and (C)2) The total amount of the anion portions in the component (A) is preferably 1.0 to 10 moles, more preferably 1.2 to 8 moles, and still more preferably 1.5 to 5 moles.
In this manner, a colored cured film having high heat resistance can be obtained.
Note that (C)2) The number of moles of the anion portion in the component (A) can be determined as follows. Such as when (C)2) When the component (A) is a binary copolymer of a monomer X and a monomer Y, the structural units represented by the formulae (2) to (5) are derived from the monomer X, and the other structural units are derived from the monomer Y,
m＝WC/{WX+(Yr×WY/Xp)}. Wherein,
m：(C2) The number of moles of anions in the component (A)
WC：(C2) Mass of the ingredients
WX: molecular weight of monomer X
WY: molecular weight of monomer Y
Xp: proportion (number of moles) of structural units derived from monomer X
Yr: the proportion (number of moles) of the structural unit derived from the monomer Y.
- (D) Binder resin-
The coloring composition of the present invention may contain (D) a binder resin. This can improve the alkali solubility and storage stability of the coloring composition. The binder resin (D) is not particularly limited, and is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter, also referred to as "carboxyl group-containing polymer") is preferable, and examples thereof include a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, also referred to as "unsaturated monomer (d 1)") and another copolymerizable ethylenically unsaturated monomer (hereinafter, also referred to as "unsaturated monomer (d 2)").
Examples of the unsaturated monomer (d1) include (meth) acrylic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl ] ester, ω -carboxy polycaprolactone mono (meth) acrylate, and p-vinylbenzoic acid.
These unsaturated monomers (d1) may be used alone or in combination of 2 or more.
Further, examples of the unsaturated monomer (d2) include,
n-substituted maleimide such as N-phenylmaleimide and N-cyclohexylmaleimide;
aromatic vinyl compounds such as styrene, α -methylstyrene, p-hydroxystyrene, p-hydroxy- α -methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene;
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 2-10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2-10) 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, tricyclic [5.2.1.0 ] meth) acrylate2,6](meth) acrylates such as decan-8-yl ester, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of p-cumylphenol, glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3- [ (meth) acryloyloxymethyl ] oxetane, and 3- [ (meth) acryloyloxymethyl ] -3-ethyloxetane;
cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.02,6]Decan-8-ylvinyl ether, pentacyclopentadecaneVinyl ethers such as vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane;
polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polysiloxane, and the like.
These unsaturated monomers (d2) may be used alone or in combination of 2 or more.
In the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2), the copolymerization ratio of the unsaturated monomer (d1) in the copolymer is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (d1) in such a range, a coloring composition excellent in alkali developability and storage stability can be obtained.
Specific examples of the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2) include copolymers disclosed in, for example, Japanese patent application laid-open Nos. 7-140654, 8-259876, 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118 and 2004-101728.
In the present invention, as disclosed in, for example, Japanese patent laid-open Nos. 5-19467, 6-230212, 7-207211, 9-325494, 11-140144, 2008-181095, etc., a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in a side chain may be used as the binder resin.
The weight average molecular weight (Mw) of the binder resin in the present invention in terms of polystyrene as measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) is usually 1000 to 100000, preferably 3000 to 50000. In this manner, the film remaining rate, the pattern shape, the heat resistance, the electrical characteristics, and the resolution of the coating film can be further improved, and the generation of dry foreign matter during coating can be suppressed at a high level.
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. The Mn referred to herein is a number average molecular weight in terms of polystyrene as measured by GPC (elution solvent: tetrahydrofuran).
The binder resin of the present invention can be produced by a known method, and for example, the structure, Mw/Mn can be controlled by the methods disclosed in, for example, Japanese patent application laid-open Nos. 2003-222717, 2006-259680, and International publication No. 2007/029871 pamphlet.
In the present invention, the binder resin may be used alone or in combination of 2 or more.
In the present invention, the content of the binder resin is usually 10 to 1000 parts by mass, preferably 20 to 500 parts by mass, based on 100 parts by mass of the colorant (a). In this manner, the alkaline developability, the storage stability of the colored composition, and the chromaticity characteristics can be further improved.
Photopolymerization initiators
The coloring composition of the present invention may contain a photopolymerization initiator. This can impart radiation sensitivity to the coloring composition. The photopolymerization initiator used in the present invention is a compound which generates an active species capable of initiating polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray.
Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, bisimidazole compounds, triazine compounds, O-acyloxime compounds, and,Salt compound, benzoin compound and benzophenoneA compound, an α -diketone compound, a polynuclear quinone compound, a diazo compound, an imide sulfonate compound (イミドスルホナート compound), and the like.
In the present invention, the photopolymerization initiator may be used alone or in combination of 2 or more. As the photopolymerization initiator, at least 1 selected from the group consisting of a thioxanthone compound, an acetophenone compound, a bisimidazole compound, a triazine compound, and an O-acyloxime compound is preferable.
Among the preferable photopolymerization initiators in the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-dichlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, and 2, 4-diisopropylthioxanthone.
Specific examples of the acetophenone compound include 2-methyl-1- [ 4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.
Specific examples of the biimidazole compound include 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4-dichlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -biimidazole, and 2,2 '-bis (2,4, 6-trichlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -biimidazole.
In the case of using a biimidazole compound as a photopolymerization initiator, it is preferable to use a hydrogen donor in combination from the viewpoint of improving sensitivity. The "hydrogen donor" as used herein refers to a compound capable of supplying a hydrogen atom to a radical generated from a bisimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoThiol hydrogen donors such as oxazole, 4,4 '-bis (dimethylamino) benzophenone, 4,4' -bis (diethylamino) benzophenoneAnd amine hydrogen donors such as methanones. In the present invention, the hydrogen donors may be used alone or in combination of 2 or more, but from the viewpoint of further improving the sensitivity, it is preferable to use 1 or more thiol hydrogen donors and 1 or more amine hydrogen donors in combination.
Further, specific examples of the triazine compounds include 2,4, 6-tris (trichloromethyl) -s-triazine, 2-methyl-4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (3, 4-dimethoxyphenyl) vinyl ] -4, triazine compounds having a halogenated methyl group such as 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, and 2- (4-n-butoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine.
Specific examples of the O-acyloxime compound include 1- [ 4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethanone 1- (O-acetyloxime), 1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl ] -ethanone 1- (O-acetyloxime), 1- [ 9-ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxolanyl) methoxybenzoyl } -9H-carbazol-3-yl ] -ethanone 1- (O-acetyloxime), and the like. As commercially available O-acyloxime compounds, NCI-831, NCI-930 (manufactured by ADEKA Co., Ltd.), DFI-020, and DFI-091 (manufactured by daitochemix Co., Ltd.) can be used.
In the present invention, when a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination. Examples of such sensitizers include 4,4 '-bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminoprophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, and 4- (diethylamino) chalcone.
In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, and particularly preferably 1 to 100 parts by mass, based on 100 parts by mass of the polymerizable compound (B). This configuration can further improve curability and film properties.
-solvent-
The coloring composition of the present invention contains the above-mentioned components (a) to (C) and optionally other components, and is usually prepared as a liquid composition by blending a solvent.
The solvent may be appropriately selected and used as long as it is capable of dispersing or dissolving the components (a) to (C) and other components constituting the coloring composition, does not react with these components, and has appropriate volatility.
Among such solvents, for example:
(poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl 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, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc.;
alkyl lactate esters such as methyl lactate and ethyl lactate;
(cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol and cyclohexanol;
ketone alcohols such as diacetone alcohol;
(poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate;
other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran;
ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;
diacetates such as propylene glycol diacetate, 1, 3-butanediol diacetate, and 1, 6-hexanediol diacetate;
alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutylpropionate;
other esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate;
aromatic hydrocarbons such as toluene and xylene;
amides and lactams such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Among these solvents, from the viewpoints of solubility, pigment dispersibility, coatability and the like, (poly) alkylene glycol monoalkyl ethers, alkyl lactate esters, (poly) alkylene glycol monoalkyl ether acetates, other ethers, ketones, diacetate esters, alkoxycarboxylic acid esters and other esters are preferable, and propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene 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-butanediol diacetate, 1, 6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, methyl 1, 6-hexanediol diacetate, ethyl lactate, ethyl 3-ethoxypropionate, ethyl 3-methyl-3-methoxybutyl propionate, ethyl acetate, and the like are particularly preferable, N-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, and the like.
In the present invention, the solvent may be used alone or in combination of 2 or more.
The content of the solvent is not particularly limited, and the total concentration of the respective components other than the solvent of the coloring composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. In this manner, a colorant dispersion liquid having excellent dispersibility and stability and a coloring composition having excellent coatability and stability can be obtained.
Additives-
The coloring composition of the present invention may contain various additives as required.
Examples of the additive include fillers such as glass and alumina; high molecular weight compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); surfactants such as fluorine surfactants and silicone surfactants; adhesion promoters such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane; antioxidants such as 2, 2-thiobis (4-methyl-6-t-butylphenol), 2, 6-di-t-butylphenol, pentaerythrityl tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 3, 9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy ] -1, 1-dimethylethyl ] -2,4,8, 10-tetraoxa-spiro [ 5.5 ] undecane, and thiodiethylene bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ]; ultraviolet absorbers such as 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; a coagulation inhibitor such as sodium polyacrylate; residue improvers such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1, 2-propanediol, 2-amino-1, 3-propanediol, and 4-amino-1, 2-butanediol; developability improvers such as mono [2- (meth) acryloyloxyethyl ] succinate, mono [2- (meth) acryloyloxyethyl ] phthalate and ω -carboxy polycaprolactone mono (meth) acrylate.
Method for producing coloring composition
The coloring composition of the present invention can be produced by an appropriate method, and for example, can be produced by mixing (A) a coloring agent, (B) a polymerizable compound and (C) a compound selected from2) Component (A) and (B)1) At least 1 of the components. When both a dye and a pigment are used as the colorant, examples of the production method thereof include methods disclosed in japanese patent application laid-open nos. 2008-58642 and 2010-132874. Specifically, as disclosed in japanese patent application laid-open No. 2010-132874, the following method may be adopted: the dye solution is passed through a1 st filter, and then the dye solution passed through the 1 st filter is mixed with a separately prepared pigment dispersion liquid or the like, and the resulting colored composition is passed through a2 nd filter, thereby being prepared. In addition, the following method may be adopted: the coloring composition is prepared by dissolving the dye, the above-mentioned components (B) and (C), and other components used as needed in a solvent, passing the resulting solution through a1 st filter, mixing the solution passed through the 1 st filter with a separately prepared pigment dispersion, and passing the resulting coloring composition through a2 nd filter. In addition, the first and second substrates are,the following method may also be employed: the pigment dispersion is prepared by passing a dye solution through a1 st filter, mixing and dissolving the dye solution passed through the 1 st filter, the above-mentioned components (B) and (C) and other components used as necessary, passing the resulting solution through a2 nd filter, mixing the solution passed through the 2 nd filter with a separately prepared pigment dispersion, and passing the resulting colored composition through a3 rd filter.
In the method for producing the coloring composition of the present invention, it is preferable to contain an organic dye as the (a) colorant because the desired effect of the present invention can be easily obtained.
Colored cured film and method for producing same
The colored cured film of the present invention is formed using the colored composition of the present invention, and specifically, it refers to pixels of each color, a black matrix, a black spacer, and the like used in a color filter.
Hereinafter, a colored cured film used for a color filter and a method for forming the same will be described.
First, the following method can be used as a method for manufacturing a color filter. First, a light-shielding layer (black matrix) is formed on the surface of the substrate so as to define a portion where pixels are to be formed, as necessary. Next, a blue liquid composition of the radiation-sensitive coloring composition of the present invention is applied onto the substrate, and then, prebaked to evaporate the solvent, thereby forming a coating film. Next, the coating film is exposed through a photomask, and then developed with an alkaline developer to dissolve and remove unexposed portions of the coating film. Thereafter, a pixel array in which blue pixel patterns (colored cured films) are arranged in a predetermined array is formed by post-baking.
Next, using the respective radiation-sensitive coloring compositions of green or red, coating, prebaking, exposure, development, and postbaking of the respective radiation-sensitive coloring compositions were performed in the same manner as described above, and a pixel array of green and a pixel array of red were formed in this order on the same substrate. Thus, a color filter in which a pixel array of three primary colors of blue, green, and red is arranged on a substrate is obtained. In the present invention, the order of forming each color pixel is not limited to the above order.
The black matrix may be formed by forming a thin metal film such as chromium formed by sputtering or vapor deposition into a desired pattern by photolithography, or may be formed by using a radiation-sensitive coloring composition in which a black pigment is dispersed, in the same manner as in the case of forming the pixels.
Examples of the substrate used for forming a color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide-imide, and polyimide.
If necessary, these substrates may be subjected to appropriate pretreatment such as reagent treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like.
When the radiation-sensitive coloring composition is applied to a substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method (slit coating method), a bar coating method, or the like can be used, and the spin coating method and the slit die coating method are particularly preferably used.
The prebaking is generally performed in combination of drying under reduced pressure and drying by heating. The drying under reduced pressure is usually carried out until 50 to 200Pa is reached. The conditions for the heat drying are usually about 70 to 110 ℃ for 1 to 10 minutes.
The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, in terms of the film thickness after drying.
Examples of the light source of the radiation used when at least 1 kind selected from the group consisting of the pixels and the black matrix is formed include lamp light sources such as 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 mercury lamp, and laser light sources such as an argon ion laser, a YAG laser, an XeCl excimer laser, and a nitrogen laser. As the exposure light source, an ultraviolet LED may be used. Radiation having a wavelength of 190 to 450nm is preferable.
The exposure amount of the radiation is preferably 10 to 10000J/m2。
The above-mentioned alkaline developer is preferably an aqueous solution of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1, 8-diazabicyclo- [5.4.0] -7-undecene, 1, 5-diazabicyclo- [4.3.0] -5-nonene, or the like.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkaline developer. After the alkaline development, washing with water is usually performed.
As the developing method, a spray developing method, a dip (dip) developing method, a spin-on-immersion (puddle) developing method, or the like can be applied. The developing conditions are preferably normal temperature and 5-300 seconds.
The post-baking conditions are usually 180 to 280 ℃ for about 10 to 60 minutes.
The thickness of the pixel formed in this way is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.
Further, as a second method for manufacturing a color filter, a method of obtaining each color pixel by an ink jet method disclosed in japanese patent laid-open nos. 7-318723 and 2000-310706, and the like can be adopted. In this method, first, a partition wall having a light shielding function is formed on a surface of a substrate. Next, a liquid composition such as a blue colored thermosetting coloring composition of the present invention is discharged into the formed partition wall by an ink jet device, and then, prebaking is performed to evaporate the solvent. Next, the coating film is exposed to light as necessary, and then cured by post baking to form a blue pixel pattern.
Next, a green pixel pattern and a red pixel pattern are formed in this order on the same substrate using the respective thermosetting coloring compositions for green and red, in the same manner as described above. Thus, a color filter in which pixel patterns of three primary colors of blue, green, and red are arranged on a substrate is obtained. In the present invention, the order of forming each color pixel is not limited to the above order.
The partition walls have a thicker film thickness than the black matrix used in the first method, because they function not only to shield light but also to prevent color mixing of the thermosetting coloring composition of each color discharged into the cells. Therefore, the partition wall is usually formed using a black radiation-sensitive composition.
The substrate, the light source of the radiation, and the methods and conditions for the pre-baking and the post-baking used in forming the color filter are the same as those in the first method. In this way, the film thickness of the pixel formed by the ink jet method is approximately equal to the height of the partition.
After a protective film is formed as necessary on the pixel pattern obtained in this way, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, and may be a light-shielding spacer (black spacer). In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for forming the black spacer.
The colored composition of the present invention can be suitably used for forming any colored cured film of pixels of various colors, black matrices, black spacers, and the like used for the above color filters.
The color filter containing the colored cured film of the present invention formed in this way is extremely high in luminance and coloring power, and is therefore extremely useful for color liquid crystal display elements, color image tube elements, color sensors, organic EL display elements, electronic paper, and the like. The display element described later may be provided with at least 1 or more colored cured films formed using the colored composition of the present invention.
Display element
The display element of the present invention includes the colored cured film of the present invention. Examples of 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 transmissive or reflective, and may have an appropriate structure. For example, a configuration may be adopted in which a color filter is formed on a substrate different from a driving substrate on which a Thin Film Transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed face each other with a liquid crystal layer interposed therebetween; a structure may be employed in which a substrate on which a color filter is formed on a surface of a driving substrate on which a Thin Film Transistor (TFT) is disposed and a substrate on which an ITO (indium oxide doped with tin) electrode is formed are opposed to each other with a liquid crystal layer interposed therebetween. The latter structure has an advantage that the aperture ratio can be significantly increased and a bright and highly fine liquid crystal display element can be obtained. In the case of the latter structure, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed or the substrate side on which the ITO electrode is formed.
The color liquid crystal display device including the colored cured film of the present invention may include a backlight unit having a white LED as a light source, in addition to a Cold Cathode Fluorescent Lamp (CCFL). Examples of the white LED include a white LED in which a red LED, a green LED, and a blue LED are combined and white light is obtained by color mixing; a white LED which combines a blue LED, a red LED and a green phosphor and mixes the colors to obtain white light; a white LED which combines a blue LED, a red light emitting phosphor and a green light emitting phosphor and which obtains white light by color mixing; a white LED for obtaining white light by color mixing of the blue LED and the YAG phosphor; a white LED which combines a blue LED, an orange light-emitting phosphor and a green light-emitting phosphor and which mixes the light to obtain white light; and a white LED which combines an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor and mixes the light to obtain white light.
In the color liquid crystal display device including the colored cured film of the present invention, suitable liquid crystal modes such as TN (Twisted Nematic) mode, STN (Super Twisted Nematic) mode, IPS (In-plane Switching) mode, VA (Vertical Alignment) mode, and OCB (optically compensated bend Alignment) mode can be applied.
In addition, the organic EL display device including the colored cured film of the present invention may have any suitable structure, and examples thereof include those disclosed in japanese patent application laid-open No. 11-307242.
In addition, the electronic paper provided with the colored cured film of the present invention may have any suitable structure, and examples thereof include those disclosed in japanese patent application laid-open No. 2007-41169.
Examples
The embodiments of the present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples.
< Synthesis of dye >
Synthesis example 1
The following compound was obtained by referring to example 2 of the pamphlet of International publication No. 2010/123071. This was used as dye A. The dye A is a triarylmethane-based basic dye.
Synthesis example 2
The following compounds were obtained in synthesis example 1 of Japanese patent application laid-open No. 2012-107192. This was used as dye B. The dye B is a xanthene-based basic dye.
＜(C2) Synthesis of Components
Synthesis example 3
[ Synthesis of monomer (1) ]
Monomer (1) was synthesized according to the following protocol, following the procedure described below.
A300 mL four-necked flask equipped with a stirrer was charged with 100g of water, 14g (0.080 mol) of sodium dithionite and 12.1g (0.12 mol) of triethylamine, and the flask was equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. Then, a solution prepared by dissolving 9.56g (0.040 mol) of 5-bromo-4, 4,5, 5-tetrafluoropentane-1-ol in 80g of acetonitrile was added dropwise from the dropping funnel over 15 minutes while stirring. Next, the mixture was heated in an oil bath and reacted at an internal temperature of 60 ℃ for 5 hours under a nitrogen stream. After the reaction was completed, the reaction mixture was cooled to 25 ℃ and left to stand for 15 minutes, and the reaction mixture was separated into 2 layers. The organic layer was separated, 100g of acetonitrile was further added to the aqueous layer, and 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 ℃ to obtain 11.4g (0.0350 mol, yield: 88%) of a viscous oily substance. By passing1H and19F-NMR spectrum (solvent: deuterated methanol) measurement confirmed that the obtained compound was the compound represented by the above formula (1-b).
Then, 80mL of water, 60mg of sodium tungstate dihydrate and 4.5g of a 30 mass% hydrogen peroxide solution were added to the compound (1-b) obtained above, and the mixture was heated at 60 ℃ for 1 hour. After the reaction, the reaction mixture was cooled to 25 ℃ and sodium sulfite was added to decompose excess hydrogen peroxide, followed by concentration under reduced pressure. The residue was dissolved in methanol, insoluble materials were filtered off, and the resulting solution was concentrated under reduced pressure. The obtained residue was dried under reduced pressure at 50 ℃ to obtain 9.90g (0.0290 mol, yield: 83%) of a viscous oily substance. By passing1H and19F-NMR spectrum (solvent: deuterated methanol) measurement confirmed that the obtained compound was a compound represented by the above formula (1-c).
In 3A00 mL three-necked flask was equipped with a stirrer, a thermometer, and a dropping funnel, 50mL of the compound (1-c) obtained above and dichloromethane were added, and the mixture was cooled to 5 ℃ under a nitrogen stream and stirred. Thereafter, 4.33g (0.043 mol) of triethylamine was added thereto, and after stirring for a while, 3.58g (0.034 mol) of methacryloyl chloride was added dropwise over 15 minutes. Thereafter, the internal temperature was heated to 25 ℃ and stirred for 6 hours. Thereafter, the reaction mixture was poured into 100g of water to separate an organic layer, and an aqueous layer was extracted with 100g of dichloromethane. The organic layers were combined, washed 3 times with 150g of water and concentrated under reduced pressure. The obtained residue was purified by column chromatography to obtain 10.1g (0.0247 mol, yield: 85%) of a viscous oily substance. By passing1H and19F-NMR spectrum (solvent: deuterated chloroform) measurement confirmed that the obtained compound was a compound represented by the above formula. This was used as monomer (1).
[ Synthesis of Polymer (1) ]
4.50g of the monomer (1), 5.50g of methyl methacrylate, 0.713g of α -thioglycerol and 20g of cyclohexanone were mixed and dissolved uniformly. The solution was heated to 100 ℃ under a nitrogen flow with stirring. While stirring at this temperature, a solution prepared by dissolving α, α' -azobisisobutyronitrile in an amount of 10.4g of cyclohexanone in an amount of 0.541g was added dropwise over 30 minutes, and after completion of the dropwise addition, stirring was continued at this temperature for 3 hours. After the reaction solution was cooled to room temperature, 60g of acetone was added to prepare a uniform solution, and the solution was added dropwise to 1.1L of hexane. The resulting precipitate was collected by filtration and washed with hexane. The resulting solid was dried under reduced pressure at 50 ℃ to obtain 8.90g of a polymer represented by the above structural formula. The polymer obtained had Mw of 7900 and Mn of 3600 by1H-NMR spectroscopy (solvent: deuterated acetone) showed that the ratio of x to y was 1/4.91 in terms of a molar ratio (x/y). This was used as a polymer (1).
10 parts by mass of the polymer (1) and 90 parts by mass of propylene glycol monomethyl ether acetate were mixed to prepare a polymer solution (1).
Synthesis example 4
[ Synthesis of Polymer (2) ]
In the same manner as in synthesis example 1 except for using 4.57g of the following monomer (2) in place of the monomer (1) in the synthesis of the polymer (1), 7.51g of the polymer (2) represented by the above structural formula was obtained. The polymer (2) obtained had a Mw of 8600 and a Mn of 3700, obtained by1H-NMR spectroscopy (solvent: deuterated acetone) showed that the ratio of x to y was 1/4.30 in terms of a molar ratio (x/y). The monomer (2) is synthesized in accordance with synthesis example 1 of Japanese patent laid-open publication No. 2012-194466.
10 parts by mass of the polymer (2) and 90 parts by mass of propylene glycol monomethyl ether were mixed to prepare a polymer solution (2).
Synthesis example 5
[ Synthesis of Polymer (3) ]
In the same manner as in Synthesis example 1 except for using 2.39g of triethylamine vinylsulfonate salt in place of monomer (1) in the synthesis of polymer (1), 7.51g of polymer (3) represented by the above structural formula was obtained. The resulting polymer (3) had Mw of 8200 and Mn of 3800 by1H-NMR spectroscopy (solvent: deuterated acetone) confirmed that the ratio of x to y was 1/4.66 in terms of a molar ratio (x/y).
10 parts by mass of the polymer (3) and 90 parts by mass of propylene glycol monomethyl ether acetate were mixed to prepare a polymer solution (3).
< preparation of colorant solution >
Preparation example 1
Dye solution (a-1) was prepared by mixing 10 parts by mass of dye a and 90 parts by mass of propylene glycol monomethyl ether acetate.
Preparation example 2
The dye solution (a-2) was prepared by mixing 10 parts by mass of c.i. basic blue 7 (triarylmethane-based basic dye) and 90 parts by mass of propylene glycol monomethyl ether.
Preparation example 3
Dye solution (B-1) was prepared by mixing 10 parts by mass of dye B and 90 parts by mass of propylene glycol monomethyl ether.
< Synthesis of Binder resin >
Synthesis example 6
100 parts by mass of propylene glycol monomethyl ether acetate was charged into a flask equipped with a cooling tube and a stirrer, and nitrogen substitution was performed. Heating to 80 ℃, dropping a mixed solution of 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, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono (2-acryloyloxyethyl) succinate and 6 parts by mass of 2,2' -azobis (2, 4-dimethylvaleronitrile) at that temperature for 1 hour, and polymerizing for 2 hours while maintaining the temperature. Thereafter, the temperature of the reaction solution was raised to 100 ℃ and polymerization was further carried out for 1 hour, whereby a binder resin solution (solid content concentration 33 mass%) was obtained. The resulting binder resin had a Mw of 12200 and Mn of 6500. This binder resin was referred to as "binder resin (D1)".
< preparation of pigment Dispersion >
Preparation example 4
A pigment dispersion (a-1) was prepared by treating the following reagent, c.i. pigment blue 15 as a colorant, with a bead mill: 12 parts by mass of a mixture of 6/c.i. pigment violet 23 ═ 80/20 (mass ratio), 8.3 parts by mass of BYK2001 (Disperbyk: BYK-chemie (BYK) corporation, nonvolatile content: 46 mass%) as a dispersant, and Solsperse12000 as a dispersion aid: 0.8 part by mass, and 78.9 parts by mass of propylene glycol monomethyl ether acetate as a solvent.
< preparation and evaluation of coloring composition >
Example 1
13.5 parts by mass of a pigment dispersion (a-1) as a colorant, 7.2 parts by mass of a dye solution (A-1), 30.0 parts by mass of a binder resin (D1) solution as a binder resin (D), 13.7 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as a polymerizable compound (B) (product name KAYARAD DPHA, manufactured by Nippon chemical Co., Ltd.) and (C) were mixed together1) A colored composition (S-1) having a solid content of 20 mass% was prepared from 0.40 mass parts of trifluoromethanesulfonamide as component (A), 1.8 mass parts of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name IRGACURE 369, Ciba Specialty Chemicals) as a photopolymerization initiator, 0.1 mass parts of NCI-930 (manufactured by ADEKA Co., Ltd.), 0.05 mass parts of MEGAFAC F-554 (manufactured by DIC) as a fluorine-based surfactant, and propylene glycol monomethyl ether acetate as a solvent.
Evaluation of Heat resistance
SiO formed on surface by spin coater for preventing sodium ion from dissolving out2After coating the colored composition (S-1) on the soda glass substrate, the substrate was prebaked at 90 ℃ for 2 minutes to form a coating film having a thickness of 2.5. mu.m.
Subsequently, the substrate was cooled to room temperature, and then, 400J/m was measured using a high-pressure mercury lamp through a photomask2The exposure amount of (A) is an amount for exposing each coating film to radiation including wavelengths of 365nm, 405nm and 436 nm. Thereafter, the resultant was subjected to development pressure of 1kgf/cm2(nozzle holderDiameter 1mm) was sprayed onto these substrates with a developing solution consisting of 0.04 mass% potassium hydroxide aqueous solution at 23 ℃ to carry out 90-second shower development. Thereafter, the substrate was washed with ultrapure water, air-dried, and then baked in a clean oven at 200 ℃ for 30 minutes, thereby forming a dot pattern on the substrate.
The obtained dot pattern was measured for chromaticity coordinate values (x, Y) and stimulus value (Y) in the CIE color system with a C light source and a 2-degree visual field using a color analyzer (MCPD 2000, manufactured by luka electronics corporation).
Subsequently, the substrate was additionally baked at 230 ℃ for 90 minutes, and then chromaticity coordinate values (x, Y) and stimulus values (Y) were measured to evaluate the color change before and after the additional baking, i.e., Δ E* ab. As a result,. DELTA.E* abA value of (b) is less than 2.0, a value of 2.0 or more and less than 3.0 is evaluated as "very good", a value of 3.0 or more and less than 5.0 is evaluated as "Δ", and a value of 5.0 or more is evaluated as "x". The evaluation results are shown in table 1. Note that Δ E can be said* abThe smaller the value, the better the heat resistance.
Examples 2 to 4 and comparative examples 1 and 2
In example 1, the kind of dye solution and/or (C) was changed as shown in Table 11) A coloring composition was prepared in the same manner as in example 1, except for the contents of the components. Subsequently, the heat resistance was evaluated in the same manner as in example 1. The results are shown in Table 1.
TABLE 1
Examples 5 to 8
In example 1, (C) shown in Table 2 was used2) Component (C) is substituted1) Other than the components, a coloring composition was prepared in the same manner as in example 1. Subsequently, the heat resistance was evaluated in the same manner as in example 1. The results are shown in Table 2.
TABLE 2

Claims (7)

1. A coloring composition comprising (A) a coloring agent, (B) a polymerizable compound, and (C)2) Any 1 or more kinds of polymers having a structural unit represented by the following formula (2), (3), (4) or (5),
in the formulae (2) to (5),
R1、R11、R21and R31Each independently represents a methyl group, a trifluoromethyl group or a hydrogen atom,
R12and R13Each independently represents a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group,
Rfrepresents a hydrogen atom, a halogen group, or a substituted or unsubstituted hydrocarbon group, at least one RfIs a fluorine atom or an alkyl group having a fluorine atom,
y represents a 2-valent group or a single bond,
d represents a 2-valent organic group,
w represents a halogen group, a halogenated hydrocarbon group, or a 1-valent group having a linking group containing an atom other than a carbon atom, a hydrogen atom, or a halogen atom between C-C bonds of the halogenated hydrocarbon group,
a represents a 2-valent group or a single bond,
g represents a 2-valent organic group containing a fluorine atom or a single bond,
ar represents a substituted arylene group having at least 1 or more halogen groups,
e represents a 2-valent group or a single bond,
Xm+represents a proton,A cation or a metal ion, and a metal ion,
m represents a natural number of 1 to 3,
n represents an integer of 0 to 3,
p represents an integer of 1 to 8.
2. The coloring composition according to claim 1, wherein (C)2) The content of the polymer having a structural unit represented by the formula (2), (3), (4) or (5) is 10 to 500 parts by mass with respect to 100 parts by mass of the colorant (A).
3. A coloring composition comprising (A) a coloring agent, (B) a polymerizable compound, and (C)1) A compound represented by the following formula (1) and (D) a binder resin,
X+(ZaR0 bM)-(1)
in the formula (1), the reaction mixture is,
X+represents a proton,A cation or an alkali metal ion, and a salt thereof,
z represents an electron-withdrawing group,
R0represents an alkyl, aryl, cycloalkyl or alkylaryl group,
m represents a nitrogen atom, a phosphorus atom, a boron atom, an arsenic atom or an antimony atom,
a represents an integer of 1 to 6,
b represents an integer of 0 to 5,
wherein a + b is 2,4 or 6, Z, R0When a plurality of the compounds are present, they may be the same or different.
4. The coloring composition according to any one of claims 1 to 3, wherein the (A) colorant contains a dye.
5. A process for producing a coloring composition comprising mixing (A) a coloring agent, (B) a polymerizable compound and (C) a component selected from the group consisting of2) Component (A) and (B)1) At least 1 of the ingredients.
6. A colored cured film formed by using the colored composition according to any one of claims 1 to 4.
7. A display device comprising the colored cured film according to claim 6.
CN201410575556.3A 2013-10-25 2014-10-24 Coloring composition, colored cured film, and display element Active CN104570600B (en)

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