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CN108047749B - Colored resin composition, color filter, liquid crystal display device, and organic EL display device - Google Patents

Colored resin composition, color filter, liquid crystal display device, and organic EL display device Download PDF

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CN108047749B
CN108047749B CN201810026084.4A CN201810026084A CN108047749B CN 108047749 B CN108047749 B CN 108047749B CN 201810026084 A CN201810026084 A CN 201810026084A CN 108047749 B CN108047749 B CN 108047749B
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resin composition
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CN108047749A (en
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藤原宗贤
蓼沼祥平
西村政昭
相马实
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Mitsubishi Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
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    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
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    • 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
    • C09B11/26—Triarylmethane dyes in which at least one of the aromatic nuclei is heterocyclic
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    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3617—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
    • C09B29/3621—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring
    • C09B29/3626—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more hydroxyl groups (or = O)
    • C09B29/363—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more hydroxyl groups (or = O) from diazotized amino carbocyclic rings
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    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3617—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
    • C09B29/3621—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring
    • C09B29/3626—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more hydroxyl groups (or = O)
    • C09B29/3634—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more hydroxyl groups (or = O) from diazotized heterocyclic rings
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    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
    • C09B33/02—Disazo dyes
    • C09B33/12—Disazo dyes in which the coupling component is a heterocyclic compound
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    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or dyes
    • C09B67/0008—Coated particulate pigments or dyes with organic coatings
    • C09B67/0009—Coated particulate pigments or dyes with organic coatings containing organic acid derivatives
    • C09B67/001—Coated particulate pigments or dyes with organic coatings containing organic acid derivatives containing resinic acid derivatives
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
    • C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
    • C09B69/06—Dyestuff salts, e.g. salts of acid dyes with basic dyes of cationic dyes with organic acids or with inorganic complex acids
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]

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  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The present invention aims to provide a high-quality display, and a colored resin composition that can suppress the deterioration of the image quality of the display, and further aims to provide a color filter having excellent color purity and transmittance of pixels, and a high-quality liquid crystal display device and an organic EL display device, by using such a colored resin composition. To this end, the present invention provides a colored resin composition comprising (a) a dye, (B) a solvent, (C) a binder resin, and (D) a chain transfer agent, wherein (D) the chain transfer agent contains a specific compound.

Description

Colored resin composition, color filter, liquid crystal display device, and organic EL display device
The present application is a divisional application of applications entitled "colored resin composition, color filter, liquid crystal display device, and organic EL display device" having an application date of 2012, 3/22/2012 and an application number of 201280014500. X.
Technical Field
The invention relates to a colored resin composition, a color filter, a liquid crystal display device and an organic EL display device.
Background
In recent years, attention has been paid to a color liquid crystal display device and an organic EL (Electroluminescence) display as flat panel displays, and color filters are used for these displays.
For example, as an example of a color liquid crystal display device, there is a transmissive liquid crystal display device basically composed of a color filter substrate having a black matrix, a colored layer including a plurality of colors (usually three primary colors of red (R), green (G), and blue (B)), a transparent electrode, and an alignment layer, a counter electrode substrate, and a liquid crystal layer; the counter electrode substrate has a thin film transistor (TFT element), a pixel electrode, and an alignment layer; the liquid crystal layer is formed by disposing the two substrates to face each other with a predetermined gap therebetween, sealing the substrates with a sealing member, and injecting a liquid crystal material into the gap. In addition, there is a reflective liquid crystal display device in which a reflective layer is provided between the color filter substrate and the color layer.
Color filters are required to have improved color purity, chroma, and light transmittance.
In the past, in order to achieve the purpose of improving the light transmission amount, the following methods were adopted: a method of reducing the content of the coloring pigment with respect to the photosensitive resin in the image forming material; or a method of making a pixel formed of an image forming material thin.
However, these methods cause a reduction in the chroma of the color filter itself, and as a result, cause problems such as the entire display becoming white and insufficient color definition required for display.
On the other hand, if the content of the coloring pigment is increased in consideration of the chroma, the display becomes dark as a whole, and in this case, the amount of light from the backlight needs to be increased to secure the brightness, which causes a problem that the power consumption of the display increases.
In order to achieve an improvement in light transmittance, a method of finely dispersing pigment particles to a particle size of 1/2 or less having a color development wavelength is known (non-patent document 1), but such a method requires further fine dispersion than the conventional method, and thus increases the cost and the stability after dispersion are problematic.
On the other hand, color filters using dyes as color materials have also been developed. For example, as a colored resin composition for forming Blue pixels, patent document 1 discloses a color filter provided with a Blue filter layer containing c.i. acid Blue 83 (triallylamine pigment) and c.i. solvent Blue 67 (copper phthalocyanine pigment).
In addition, as a colored resin composition for forming green pixels, patent document 2 discloses the following: in forming the green pixel, a colored resin composition containing a zinc phthalocyanine pigment and a yellow dye is used.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2002-14222
Patent document 2: japanese laid-open patent publication No. 2010-168531
Non-patent document
Non-patent document 1: qiaojiaqing (journal of society of color and Material) (Gezai ) (1967, 12 months, p 608)
Disclosure of Invention
Problems to be solved by the invention
However, the colored resin composition for forming blue pixels described in patent document 1 is insufficient in suppressing the entire display from turning white and suppressing the deterioration of the image quality of the display, such as insufficient color definition required for display.
The colored resin composition for forming green pixels described in patent document 2 is not sufficient in terms of pixel formation and developability.
The present invention has been made in view of the above problems, and an object thereof is to provide a display having excellent pixel formation and development properties and high image quality, and to provide a colored resin composition which can suppress deterioration in image quality of the display.
Further, it is an object of the present invention to provide a color filter having excellent color purity and transmittance of pixels, and a high-quality liquid crystal display device and an organic EL display device using such a colored resin composition. Means for solving the problems
The present inventors have conducted intensive studies and, as a result, have found that: when a dye is used as the color material, insufficient curing of the surface of the formed pixel and low solvent resistance of the pixel are one of the causes of deterioration of image quality of the display.
The solvent resistance of the pixel is a property that characterizes the difficulty of dissolution of a color material (pigment or dye) contained in the formed pixel in a solvent.
That is, if the solvent resistance of the pixel is insufficient, for example, when an alignment film or a protective coating layer is formed by coating, it is estimated that a color material contained in the pixel is eluted into a solvent contained in a composition for forming the alignment film or the protective coating layer, and a liquid crystal layer formed on the alignment film or the protective coating layer is contaminated, thereby deteriorating the image quality of the display.
The reason why the solvent resistance is likely to decrease when a dye is used as the coloring material is further presumed as follows.
It has been found that, in the case where a dye is contained, even if the photopolymerization initiator becomes excited upon receiving light energy at the time of exposure, the photopolymerization initiator transfers energy to the dye before generating radicals due to contact with the dye, and this may cause a part of the photopolymerization initiator to fail to exert a function of generating radicals.
The above phenomena that occur when dyes are used can be attributed to: in the colored resin composition, the probability of contact between the dye existing substantially in a monomolecular state and the photopolymerization initiator is higher than that of the pigment formed by associating the coloring material. That is, in the case where the dye is contained, the probability that the energy of the photopolymerization initiator is transferred is higher than that in the case where the pigment is contained. From this, it can be presumed that: when a dye is contained, the photopolymerization initiator does not sufficiently exert an action of generating radicals, and the solvent resistance is lowered, as compared with the case of using a pigment, and in some cases, the pixel formability is insufficient.
As a result of further intensive studies based on the above findings, it has been found that the above problems can be solved by including a specific compound in a colored resin composition containing a dye, and the present invention has been completed.
That is, the present invention relates to the following colored resin composition, color filter, liquid crystal display device, and organic EL display device.
[1] A colored resin composition comprising (A) a dye, (B) a solvent, (C) a binder resin, and (D) a chain transfer agent, wherein the chain transfer agent (D) comprises a compound represented by the following formula (I) (hereinafter, sometimes referred to as "compound (I)").
[ chemical formula 1]
Figure BDA0001544982900000041
(in the formula (I), p represents an integer of 2 to 4.
Ra1Represents a hydrogen atom or an alkyl group optionally having a substituent.
X represents a direct bond, a 2-4-stage carbon atom, a 2-4-valent heterocyclic group or a 2-4-valent aromatic ring group.
The structures represented by the following formula (I') contained in one molecule may be the same or different. )
[ chemical formula 2]
Figure BDA0001544982900000042
[2] The colored resin composition according to [1], wherein the content of the chain transfer agent (D) is 2 to 10% by weight based on the total solid content.
[3] The colored resin composition according to [1] or [2], wherein the dye is a triarylmethane-based dye.
[4] The colored resin composition according to any one of the above [1] to [3], further comprising (E) a polymerizable monomer.
[5] The colored resin composition according to [4], wherein the polymerizable monomer (E) is a compound having an ethylenically unsaturated double bond.
[6] The colored resin composition according to any one of the above [1] to [5], further comprising (F) at least one of a photopolymerization initiating component and a thermal polymerization initiating component.
[7] A color filter comprising a pixel formed using the colored resin composition according to any one of [1] to [6 ].
[8] A liquid crystal display device having the color filter according to [7 ].
[9] An organic EL display device having the color filter according to [7 ].
ADVANTAGEOUS EFFECTS OF INVENTION
By using the colored resin composition of the present invention, a pixel having excellent pixel formability and developability and high solvent resistance can be formed. Thus, a liquid crystal display device including pixels formed using the colored resin composition of the present invention has high image quality.
Further, by obtaining a color filter having excellent color purity and transmittance of pixels and using such a color filter, a liquid crystal display device and an organic EL display device can be provided which can efficiently lead out light emission of a backlight of the color filter and achieve both high color reproducibility and high luminance.
Drawings
FIG. 1 is a schematic cross-sectional view showing an example of an organic EL element including a color filter of the present invention.
Description of the symbols
100 organic EL element
20 pixels
30 organic protective layer
40 inorganic oxide film
500 organic light-emitting body
51 hole injection layer
54 electron injection layer
Detailed Description
The embodiments of the present invention will be described in detail below, but the following description is only an example of the embodiments of the present invention, and the present invention is not limited to these contents.
In the present specification, "mass%" and "wt%", "mass ppm" and "wt ppm", and "parts by mass" and "parts by weight" are synonymous, respectively. In addition, the term "ppm" means "ppm by weight".
In the present invention, "(meth) acryloyl group", "meth (acrylate)" and the like mean "acryloyl group and/or methacryloyl group", "acrylate ester and/or methacrylate ester" and the like, and for example, "(meth) acrylic acid" means "acrylic acid and/or methacrylic acid".
In addition, the "total solid content" means: the colored resin composition for a color filter of the present invention contains all components except a solvent component described later.
Further, the "aromatic ring" means: both "aromatic hydrocarbon ring" and "aromatic heterocycle".
The colored resin composition of the present invention contains (a) a dye, (B) a solvent, (C) a binder resin, and (D) a compound (I) as a chain transfer agent, and preferably further contains (E) a polymerizable monomer, (F) a photopolymerization initiating component and/or a thermal polymerization initiating component, and if necessary, other components.
First, the chain transfer agent (D) contained in the colored resin composition of the present invention will be described.
[ (D) chain transfer agent ]
The chain transfer agent (D) in the present invention means: a compound having a function of accepting the generated radical and transferring the radical to other compounds.
The colored resin composition of the present invention contains a compound represented by the following formula (I) as the (D) chain transfer agent.
[ chemical formula 3]
Figure BDA0001544982900000061
(in the formula (I), p represents an integer of 2 to 4.
Ra1Represents a hydrogen atom or an alkyl group optionally having a substituent.
X represents a direct bond, a 2-4-stage carbon atom, a 2-4-valent heterocyclic group or a 2-4-valent aromatic ring group.
The structures represented by the following formula (I') contained in one molecule may be the same or different. )
[ chemical formula 4]
Figure BDA0001544982900000062
(with respect to R)a1)
Ra1Represents a hydrogen atom or an alkyl group optionally having a substituent.
The alkyl group has usually 1 to 8 carbon atoms, and particularly preferably 1 or 2 carbon atoms.
As Ra1Hydrogen atoms are preferred because of high reactivity of the compound and high surface curability of the resulting film.
R is defined asa1Examples of the substituent optionally having alkyl in (b) include the following (substituent group W)1) The group described in the above paragraph.
(substituent group W)1)
Fluorine atom, chlorine atom, alkenyl group having 2 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, phenyl group,
Figure BDA0001544982900000071
A tolyl group, a naphthyl group, a cyano group, an acetoxy group, an alkylcarboxyl group having 2 to 9 carbon atoms, a sulfonamide group, an alkylsulfamoyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetamido group, a dialkylaminoethyl group having 1 to 4 carbon atoms bonded thereto, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, a trialkylsilyl group having 1 to 8 carbon atomsAlkylthio groups of (2).
(about X)
In the formula (I), X represents a direct bond, a 2-4-order carbon atom, a 2-4-valent heterocyclic group or a 2-4-valent aromatic ring group.
The case where X is a 2-4 carbon atom means a case where X has any of the following structures.
[ chemical formula 5]
Figure BDA0001544982900000072
Examples of the aromatic ring group in X include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
The aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 5 to 18, and examples thereof include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, perylene,
Figure BDA0001544982900000073
A ring, a benzophenanthrene ring, an acenaphthylene ring, a benzoacenaphthylene ring, a fluorene ring, etc.
The free valence in the present invention is described in the nomenclature of organic chemistry/biochemistry (southern Jiantang, 20 th.5.1992, Jian-III, Ping-shan and Xiong-Ming-Dynasty, pages 11 to 12).
The aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 3 to 10, and examples thereof include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, or the like,
Figure BDA0001544982900000074
A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring
Figure BDA0001544982900000075
An azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring,
Figure BDA0001544982900000076
A pyridine ring, a quinazoline ring, a quinazolinone ring, a,
Figure BDA0001544982900000077
Rings, and the like.
On the other hand, the heterocyclic group (i.e., non-aromatic heterocyclic group) may be a monocyclic ring or a condensed ring.
The heterocyclic group is a non-aromatic ring containing any one of a nitrogen atom, a sulfur atom and an oxygen atom as a hetero atom.
When the heterocyclic group has a plurality of hetero atoms constituting a ring, these hetero atoms may be the same or different.
Specific examples thereof include: pyridyl, quinolyl, isoquinolyl, benzothiazolinyl, phthalimidyl, piperidyl, pyrrolidinyl, and the like.
Among X, a carbon atom of 2 to 4 stages is preferable, and a carbon atom of 4 stages (quaternary carbon atom) is particularly preferable, from the viewpoint of good storage stability of the compound (I).
The carbon atom, heterocyclic group and aromatic ring group in X may have a substituent other than the group represented by the following structural formula (I') (hereinafter, may be referred to as "mercapto group-containing structure"), and examples of the substituent include those described above (substituent group W)1) The group described in the above paragraph.
[ chemical formula 6]
Figure BDA0001544982900000081
(concerning p)
P represents an integer of 2 to 4.
In the compound (I), when the number of mercapto groups as reaction sites is increased, the reactivity of the compound is improved and the curability of the resulting pixel is sufficient, and from this point of view, it is particularly preferable that p is 4.
Specific examples of the compound (I) in the present invention are shown below, but the present invention is not limited to these examples.
[ specific examples of Compound (I) ]
A compound having 2 thiol-containing structures: 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 4-butanedithiol, 2, 3-butanedithiol, 1, 5-pentanethiol, 1, 6-hexanedithiol, 1, 8-octanethiol, 1, 9-nonanedithiol, 2, 3-dimercapto-1-propanol, dithioerythritol, 1, 2-benzenedithiol, 1, 2-benzenedimethylthiol, 1, 3-benzenedithiol, 3, 4-dimercaptotoluene, 4-chloro-1, 3-benzenedithiol, 2-hexylamino-4, 6-dimercapto-1, 3, 5-triazine, 2-diethylamino-4, 6-dimercapto-1, 3, 5-triazine, 2-cyclohexylamino-4, 6-dimercapto-1, 3, 5-triazine, ethylene glycol bis (3-mercaptopropionate), 2, 5-dimercapto-1, 3, 4-thiadiazole, 2-bis (2-hydroxy-3-mercaptopropoxyphenylpropane, and the like;
a compound having 3 thiol-containing structures: trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (mercaptoacetate), 1,2, 6-hexanetriol tris (mercaptoacetate), and the like;
a compound having 4 thiol-containing structures: pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), and the like.
Among the above, pentaerythritol tetrakis (3-mercaptopropionate) is particularly preferable.
(concerning the content)
The content of the chain transfer agent (D) of the present invention in the solid content of the colored resin composition is usually 2% by weight or more, preferably 4% by weight or more, and more preferably 6% by weight or more, and usually 10% by weight or less, preferably 9% by weight or less, and more preferably 8.5% by weight or less.
When the content is within the above range, the obtained pixel has sufficient curability, and the luminance of the obtained pixel is not easily affected by the decrease.
The colored resin composition of the present invention may contain a chain transfer agent other than the compound (I), and in this case, the total amount of the chain transfer agent (D) contained may be within the above range.
However, it is particularly preferable to contain only the compound (I) as the (D) chain transfer agent, and it is preferable that the content of the compound (I) is within the above range.
< reason for obtaining Effect >
The reason why the effect of suppressing the deterioration of the image quality of the obtained liquid crystal display device is obtained by adopting the configuration of the present application is presumed as follows.
As described above, one of the causes of the deterioration of the image quality of the liquid crystal display device is the insufficient solvent resistance of the resulting pixels.
Therefore, attention is paid to improvement of solvent resistance by improving curability of the obtained pixel.
In order to improve the curability of the pixel, it is necessary to sufficiently function a polymerizable curable component such as a binder resin contained in the colored resin composition.
The term "to make the polymerizable curable component function sufficiently" means that polymerization occurs in a wide range of pixels.
Conventionally, in the case of a photopolymerization system, for example, polymerization is carried out only in the vicinity of a relatively close region where a photopolymerization initiator is present, and the generated radicals are not diffused, so that it is difficult to carry out polymerization in a wide range, and curing to give a sufficient degree of solvent resistance to pixels cannot be obtained.
Here, in the present invention, by including the compound represented by the above formula (I), the generated radical can be diffused to a wide range via the compound represented by the above formula (I).
As a result, the polymerization reaction is more easily performed, and curing to a sufficient degree of solvent resistance is obtained to the pixels, thereby suppressing the deterioration of the image quality of the liquid crystal display device.
[ (A) dye ]
The dye (a) in the present invention is not particularly limited insofar as the effect of the present invention is not impaired, and preferable examples thereof include: azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, cyanine dyes, triarylmethane dyes, and the like.
As azo dyes, there may be mentioned, for example: c.i. acid yellow 11, c.i. acid orange 7, c.i. acid red 37, c.i. acid red 180, c.i. acid blue 29, c.i. direct red 28, c.i. direct red 83, c.i. direct yellow 12, c.i. direct orange 26, c.i. direct green 28, c.i. direct green 59, c.i. active yellow 2, c.i. active red 17, c.i. active red 120, c.i. active black 5, c.i. disperse orange 5, c.i. disperse red 58, c.i. disperse blue 165, c.i. basic blue 41, c.i. basic red 18, c.i. medium red 7, c.i. medium yellow 5, c.i. medium black 7, etc.
Examples of the anthraquinone-based dye include: c.i. vat blue 4, c.i. acid blue 40, c.i. acid green 25, c.i. active blue 19, c.i. active blue 49, c.i. disperse red 60, c.i. disperse blue 56, c.i. disperse blue 60, etc.
Further, as phthalocyanine-based dyes, for example: c.i. vat blue 5, etc.; examples of the quinoneimine-based dye include: c.i. basic blue 3, c.i. basic blue 9, and the like; examples of quinoline dyes include: c.i. solvent yellow 33, c.i. acid yellow 3, c.i. disperse yellow 64, and the like; examples of the nitro dye include: c.i. acid yellow 1, c.i. acid orange 3, c.i. disperse yellow 42, and the like.
Among these, the most suitable dyes vary depending on the desired pixel color.
In the case of forming a blue pixel, a triarylmethane dye and a cyanine dye are preferable, and a triarylmethane dye is particularly preferable, from the viewpoint of high luminance of the resulting pixel.
In the case of a triarylmethane dye, the effect of the present invention is more easily obtained, and therefore, the triarylmethane dye is preferable.
In the case of forming a red pixel and a green pixel, an azo-based yellow dye is particularly preferable in terms of easily obtaining the effects of the present invention with respect to the yellow dye used as a complementary color thereof.
First, a dye suitable for use in the colored resin composition for forming blue pixels, that is, a triarylmethane dye and a cyanine dye will be described in detail.
[ triarylmethane-based dyes ]
(triarylmethane dye: a compound represented by the formula (II))
The triarylmethane-based dye is particularly preferably a compound represented by the following formula (II) (hereinafter, may be referred to as "compound (II)") in view of excellent heat resistance and excellent blue color purity and transmittance of the obtained pixel.
[ chemical formula 7]
Figure BDA0001544982900000111
(in the above formula (II), Zm1-Represents m1 valent anion.
m1 represents an integer of 1 to 4.
R1～R6Each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted aromatic ring group. Adjacent R1～R6The ring may be bonded to each other to form a ring. In addition, the ring optionally has a substituent.
R7And R8Represents a hydrogen atom or an optional substituent. R7And R8The rings may be connected to each other to form a ring.
In addition, the benzene ring in the above formula (II) may further have an optional substituent.
When a plurality of structures represented by chemical formula 8 are contained in one molecule, they may be the same structure or different structures. )
[ chemical formula 8]
Figure BDA0001544982900000112
(with respect to R)1～R6)
R1～R6Each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted aromatic ring group.
As R1～R6Examples of the alkyl group in (3) include a linear, branched or cyclic alkyl group having usually not less than 1 carbon atom, usually not more than 8 carbon atoms, and preferably not more than 5 carbon atoms. Specific examples thereof include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, and cyclohexyl.
As R1～R6The aromatic ring in (1) includes an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
The aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 5 to 18, and examples thereof include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, perylene,
Figure BDA0001544982900000124
A ring, a benzophenanthrene ring, an acenaphthylene ring, a benzoacenaphthylene ring, a fluorene ring, etc.
The aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 3 to 10, and examples thereof include: a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a thiophene,
Figure BDA0001544982900000125
A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring
Figure BDA0001544982900000126
An azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline (cinnoline) ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a pyridine ring, a triazine ring, a quinoline ring, a phenanthridine ring, a pyridine ring,
Figure BDA0001544982900000122
A pyridine ring, a quinazoline ring, a quinazolinone ring, a,
Figure BDA0001544982900000123
A ring, etc.
Adjacent R1～R6Or may be bonded to each other to form a ring, and the ring may have a substituent.
Adjacent R1～R6When they are bonded to each other to form a ring, these rings may be bridged by a heteroatom. Specific examples of the ring include the following rings. These rings optionally have a substituent.
[ chemical formula 9]
Figure BDA0001544982900000121
From the viewpoint of chemical stability, R is preferred1～R6Each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms or an optionally substituted phenyl group, or adjacent R1～R6The dye is bonded to each other to form a ring, and more preferably an optionally substituted alkyl group having 1 to 8 carbon atoms or an optionally substituted phenyl group, from the viewpoint of improving the heat resistance of the dye and the light resistance of the obtained color filter.
R1～R6In the case of an alkyl group having 1 to 8 carbon atoms which may have a substituent, it is presumed that the charge in the cation is dispersed and the cation is stabilized by the action of the super-conjugation.
In addition, R1～R6In the case of a phenyl group optionally having a substituent, it is presumed that the charge in the cation is dispersed by extension of the conjugated system, and the cation is stabilized. Thus, it is considered that the light resistance of the color filter obtained as a result of stabilizing the cation is further improved.
As R1～R6In (1) alkyl, aromatic hydrocarbon ring group, and the group consisting of adjacent R1～R6Are bonded to each otherExamples of the substituent optionally contained in the ring to be formed include the following (substituent group W)2) The group of (1).
(substituent group W)2)
An alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkylcarbonyloxy group having 2 to 9 carbon atoms, an arylcarbonyloxy group having 7 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 9 carbon atoms, an aryloxycarbonyl group having 7 to 16 carbon atoms, a carbamoyl group, an alkylcarbamoyl group having 2 to 9 carbon atoms, an arylcarbamoyl group having 7 to 16 carbon atoms, a sulfamoyl group, an alkylaminosulfonyl group having 1 to 8 carbon atoms, an arylaminosulfonyl group having 6 to 15 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, an arylcarbonyl group having 7 to 16 carbon atoms, an alkylsulfonyl group having 1 to 8 carbon atoms, an alkylsulfonylamino group having 1 to 8 carbon atoms, an arylsulfonylamino group having 6 to 15 carbon atoms, an amino group, an alkylamino group to which an alkyl group having 1 to 8 carbon atoms is bonded, A dialkylamino group to which an alkyl group having 1 to 4 carbon atoms is bonded, an arylamino group having 6 to 15 carbon atoms, an arylalkylamino group in which an aryl group having 6 to 15 carbon atoms is bonded to an alkyl group having 1 to 4 carbon atoms, a diarylamino group to which an aryl group having 6 to 15 carbon atoms is bonded, a phenethyl group, a hydroxyethyl group, an alkylcarbonylamino group having 1 to 8 carbon atoms, an arylcarbonylamino group having 7 to 16 carbon atoms, a dialkylaminoethyl group to which an alkyl group having 1 to 4 carbon atoms is bonded, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, an arylthio group having 6 to 15 carbon atoms, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a sulfo group, a fluorine atom, a chlorine atom, or the like halogen atom.
As the above substituent group W2The aryl in (1) may be specifically mentioned as R1～R6The aromatic ring group in (1) above. The aryl group may further have the following group as a substituent: lower alkyl such as methyl and ethyl, lower alkoxy such as methoxy and ethoxy, nitro, trifluoromethyl, cyano, carbamoyl, aminosulfonyl, fluorine atom, chlorine atom and like halogen atom.
Wherein, as R1～R6The alkyl group, the aromatic ring group and the substituent optionally contained in the ring formed by the mutual connection are preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a tolyl group, an alkylcarbonyloxy group having 2 to 9 carbon atoms, a carbamoyl group, an aminosulfonyl group, an alkylaminosulfonyl group having 1 to 8 carbon atoms, a trifluoromethyl group, a cyano group, a sulfo group and a fluorine atom.
(with respect to R)7And R8)
R7And R8Represents a hydrogen atom or an optional substituent.
Examples of the optional substituent include: a halogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted aromatic ring group, or the like.
In addition, R7And R8The rings may be connected to each other to form a ring.
R7And R8When they are bonded to each other to form a ring, these may be rings bridged by a heteroatom. Specific examples of the ring include the following rings. These rings optionally have a substituent.
[ chemical formula 10]
Figure BDA0001544982900000141
(in the above, R1zAnd R2zEach independently represents a hydrogen atom or an alkyl group. )
From the viewpoint of obtaining a color filter which is blue and has high luminance, R is preferable7And R8Form a ring without bonding to each other.
In addition, the benzene ring in the above formula (II) may further have an optional substituent.
Examples of the substituent optionally contained in the benzene ring include those described above (substituent group W)2) The group described in the above paragraph.
(with respect to Z)m1-)
Zm1-Represents m1 valent anion.
The anion is not particularly limited as long as the effect of the present invention is not impaired, and examples thereof include:
F-、Cl-、Br-、I-a plasma halide ion;
(C6H5)4B-boron anions such as boron;
CH3COO-、C2H5COO-、C6H5COO-an anion of an isocarboxylic acid;
SO4 2-、HSO4 -an isocitrate anion;
HPO4 2-、PO4 3-phosphate anions such as phosphate anion;
sulfonic acid anions, and the like.
Examples of sulfonic acid anions include:
aliphatic sulfonic acid anions optionally having substituents such as trifluoromethanesulfonic acid, methanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, dodecylsulfonic acid, camphorsulfonic acid and the like;
aromatic sulfonic acid anions optionally having a substituent such as benzenesulfonic acid, p-toluenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid and the like;
anions of anthraquinone pigments having a sulfonate group such as acid blue 80(c.i.61585), acid green 25(c.i.61570), acid blue 45(c.i.63010), acid blue 43(c.i.63000), acid blue 25(c.i.62055), and acid blue 40 (c.i.65125);
anions of phthalocyanine-based coloring matters having a sulfonate group such as direct blue 86(c.i.74810) and direct blue 199 (c.i.14190);
anions of indigo pigments having a sulfonate group such as acid blue 74 (c.i.73015);
disulfonimide anions, and the like.
Among them, disulfonylimide anions are preferable, and the compound represented by the above formula (II) is particularly preferably a compound represented by the following formula (II-1).
[ chemical formula 11]
Figure BDA0001544982900000151
(in the formula, R1～R8With R in the above formula (II)1～R8The meaning is the same.
R21And R22Each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent.
In addition, R is21And R22The ring may be bonded to each other to form a ring. )
(with respect to R)21And R22)
R21And R22Each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent.
In addition, R is21And R22The ring may be bonded to each other to form a ring.
Examples of the substituent include the above-mentioned (substituent group W)2) The group described in the above paragraph.
Wherein, in particular, as R21And R22The substituent of the alkyl group, the alkenyl group or the cycloalkyl group in (b) is preferably a fluorine atom as a substituent, from the viewpoints of more uniform (non-localized) charge distribution of an anion and improvement of heat resistance of a color material.
That is, R is a group of groups in which the charge of the anion is dispersed and the anion is stabilized21And R22Preferably a C1-C8 perfluoroalkyl group.
More specifically, among the compounds represented by the above formula (II)
[ chemical formula 12]
Figure BDA0001544982900000161
The anion represented by (i) is more preferably a compound represented by the following formula (II' -1) (hereinafter, may be referred to as "anion in the compound represented by the above formula (II)").
[ chemical formula 13]
Figure BDA0001544982900000162
(in the formula (II '-1), n and n' each independently represent an integer of 1 to 8.)
n and n' are integers of 1 to 8, preferably 1 to 4.
n and n' may be the same or different.
Specific examples of the sulfonimide anion in the case where n is the same as n' include: bis (trifluoromethanesulfonyl) imide, bis (pentafluorobutanesulfonyl) imide, and the like.
Specific examples of the sulfonimide anion in which n and n' are different from each other include: pentafluoroethanesulfonyl trifluoromethanesulfonimide, trifluoromethanesulfonheptafluoropropanesulfonimide, fluorobutanesulfonyl trifluoromethanesulfonimide, and the like.
Among the above, bis (pentafluoroethanesulfonyl) imide having n ═ n' ═ 2 is particularly preferable for the reason of the most stable anion.
In another aspect, R11And R12The ring may be bonded to each other to form a ring.
In the case of forming a ring, R is particularly preferred11And R12Is a C2-12 fluoroalkylene group.
That is, the anion in the compound represented by the above formula (II-1) is more preferably an anion represented by the following formula (II' -2).
[ chemical formula 14]
Figure BDA0001544982900000171
(in the formula (II '-2), n' represents an integer of 2 to 12.)
In view of heat resistance, n' is preferably 2 to 8, and more preferably 3.
The smaller the value of n ", the smaller the influence of steric repulsion, and the stronger the interaction can be obtained. That is, it can be presumed that: the smaller n' is, the larger the interaction between the anion and the cation is, the more stable the ion pair is, and the heat resistance of the color material is improved.
Preferred specific examples of the compound represented by the formula (II) in the present invention will be shown below, but the present invention is not limited to these examples.
[ specific examples of the chemical formula Compound (II) ]
[ chemical formula 15]
Figure BDA0001544982900000181
[ chemical formula 16]
Figure BDA0001544982900000191
[ chemical formula 17]
Figure BDA0001544982900000201
(triarylmethane dye: the compound represented by the formula (III))
The triarylmethane-based dye is more preferably a compound represented by the following formula (III) (hereinafter, may be referred to as "compound (III)") in view of light resistance, heat resistance, and high transmittance.
[ chemical formula 18]
Figure BDA0001544982900000202
(in the above formula (III), Zm2-Represents m2 valent anion.
m2 represents an integer of 1 to 4.
R11～R16Each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted aromatic ring group. R11And R12、R13And R14And R15And R16Respectively can mutuallyBonded to form a ring structure.
R17And R18Each independently represents a hydrogen atom, or an optional substituent. R17And R18The ring may be bonded to each other to form a ring.
The ring and the indole ring in the formula (III) may further have an optional substituent.
When a plurality of structures represented by the following chemical formula 19 are contained in one molecule, they may have the same structure or different structures. )
[ chemical formula 19]
Figure BDA0001544982900000211
(with respect to R)11～R16)
R11～R16Each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted aromatic ring group.
Examples of the alkyl group and aromatic ring group having 1 to 8 carbon atoms include those mentioned above (with respect to R)1～R6) The same groups as those described in the above paragraph.
In addition, in adjacent R11～R16Between each other, i.e. R11And R12、R13And R14And R15And R16When they are bonded to each other to form a ring structure, they are also bonded to the above (with respect to R)1～R6) The same remarks apply to the items.
(with respect to R)17And R18)
R17And R18Represents a hydrogen atom or an optional substituent. As the optional substituent, the above-mentioned R is exemplified1～R6The group as described in (1).
In addition, R17And R18May be bonded to each other to form a ring.
R17And R18When the rings are bonded to each other to form a ring, the rings may be bonded to each other through a hetero atomThe ring formed by bridging atoms, as a specific example, with the above (for R)7And R8) The same applies to the examples described in the above section. These rings optionally have a substituent.
From the viewpoint of the color filter obtained being purple and having high luminance, R is preferred7And R8Form a ring without bonding to each other.
In addition, from the viewpoint that the obtained color filter is red and has high luminance, those in which the color filters are connected to each other to form a ring are preferable.
In the compound (III), the benzene ring and the indole ring may further have a substituent. That is, the compound may optionally have a substituent other than the substituents specifically described in the formula (III) within a range not to impair the effects of the present invention.
Examples of such a substituent include the above-mentioned (substituent group W)2) The substituent described in the above paragraph.
In the case where a large steric hindrance group is bonded to the benzene ring in the formula (III) at the ortho position relative to the bond with the carbon atom located at the center of the triarylmethine structure, the planarity of the molecule is impaired, and the color purity of the compound may be reduced. Therefore, the ortho position is preferably substituted with a halogen atom or an alkyl group having 1 to 4 carbon atoms.
In addition, the compound (III) may be, for example, R11～R18The linking group (linker) is extended to form a dimer, trimer, etc.
(Compound represented by the formula (III-1))
Among the compounds (III), the anion is particularly preferably a disulfonylimide anion, and the compound represented by the following formula (III-1) (hereinafter, sometimes referred to as "compound (III-1)") is particularly preferable for the above formula (III).
[ chemical formula 20]
Figure BDA0001544982900000221
(in the formula, R11～R18With R in the above formula (III)11～R18The same is true.
R31And R32Each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent.
In addition, R is31And R32The ring may be bonded to each other to form a ring. )
(with respect to R)31And R32)
R31And R32Each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent.
In addition, R is31And R32The ring may be bonded to each other to form a ring.
R31And R32With R in the above formula (II-1)21And R22Likewise, the preferred embodiments thereof are also the same.
That is, the anion represented by the above formula (III-1) is more preferably an anion represented by the above formula (II '-1) or (II' -2).
Preferred specific examples of the compound represented by the formula (III) in the present invention will be shown below, but the present invention is not limited to these examples.
[ specific examples of the chemical formula Compound (III) ]
[ chemical formula 21]
Figure BDA0001544982900000231
[ chemical formula 22]
Figure BDA0001544982900000241
(triarylmethane dye: a compound represented by the formula (IV))
The triarylmethane-based dye is more preferably a compound represented by the following formula (IV) (hereinafter, may be referred to as "compound (IV)") in view of high luminance and high voltage holding ratio of the resulting pixel.
[ chemical formula 23]
Figure BDA0001544982900000242
(in the above-mentioned formula,
R41～R46each independently represents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent.
Adjacent R41～R46Or may be linked to each other to form a ring, which may have a substituent.
R47And R48Each independently represents a hydrogen atom or an optional substituent.
R47And R48Or may be linked to each other to form a ring, which may have a substituent.
The benzene ring and the indole ring in the formula (IV) may further have an optional substituent.
M+Represents a hydrogen ion, an alkali metal cation, an alkaline earth metal cation, a tertiary ammonium cation or a quaternary ammonium cation.
n represents an integer of 0 to 4. )
(with respect to R)41～R46)
R41～R46Each independently represents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent.
As the alkyl group optionally having a substituent and the aromatic ring group optionally having a substituent, the above-mentioned (with respect to R) can be mentioned1～R6) The group described in the above paragraph.
From the viewpoint of improving the heat resistance of the compound (IV) and the heat resistance of the obtained color filter, an optionally substituted alkyl group having 1 to 8 carbon atoms or an optionally substituted aromatic hydrocarbon ring group having 6 to 10 carbon atoms is more preferable, and an optionally substituted alkyl group having 1 to 8 carbon atoms or an optionally substituted phenyl group is further preferable.
R41～R46When at least one of the alkyl groups is an optionally substituted alkyl group having 1 to 8 carbon atoms, it is presumed that the charge in the cation is dispersed and the cation is stabilized by the action of the super-conjugation.
In addition, R41～R46When at least one of the groups is an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, it is presumed that the charge in the cation is dispersed by extension of the conjugated system, and the cation is stabilized. Thus, it is considered that the light resistance of the color filter obtained as a result of stabilizing the cation is further improved.
Namely, R41～R46Preferably an optionally substituted alkyl group having 1 to 8 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms.
As R41～R46Examples of the alkyl group, the aromatic ring group and the substituent optionally contained in the ring formed by linking them to each other in (A) include the above (substituent group W)2) The group of (1).
(with respect to R)47And R48)
R47And R48Represents a hydrogen atom or an optional substituent. Examples of the optional substituent include: a halogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted aromatic ring group, or the like.
With respect to R47And R48With respect to R17And R18) The groups described in the above section are the same. The preferred form is the same.
(with respect to M)+And n)
M+Represents a hydrogen ion, an alkali metal cation, an alkaline earth metal cation, a tertiary ammonium cation or a quaternary ammonium cation.
As alkali metals of the alkali metal cation, there can be mentioned: lithium, sodium, potassium, and the like. In addition, as the alkaline earth metal of the alkaline earth metal cation, there may be mentioned: magnesium, calcium, barium, and the like.
Tertiary ammonium cations with N+HR3Wherein R represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aromatic ring group, wherein R may be the same or different.
Examples of the preferable number of carbon atoms and optional substituents of the alkyl group in the above-mentioned R and the above-mentioned R41～R46In the case of the alkyl group, the number of carbon atoms and the number of substituents are the same. Examples of the preferable number of carbon atoms and optional substituents of the aromatic ring group are the same as those of the above-mentioned R41～R46In the case of the aromatic ring group, the number of carbon atoms and the number of substituents are the same. Specific examples thereof include: lower alkylammonium cations having 1 to 6 carbon atoms (e.g., methylammonium cation, ethylammonium cation, diethylammonium cation, triethylammonium cation, etc.), alkylammonium cations having 1 to 6 carbon atoms substituted with a hydroxyl group (e.g., ethylammonium cation, diethanolammonium cation, triethanolammonium cation, etc.), alkylammonium cations having 1 to 6 carbon atoms substituted with a carboxyl group (e.g., carboxymethylammonium cation, carboxyethylammonium cation, carboxypropylammonium cation, dicarboxymethylammonium cation, etc.), ammonium cations substituted with an aromatic ring group and an alkyl group (e.g., N, N-diethylphenylammonium cation, etc.), and the like.
Quaternary ammonium cations with N+R4Wherein R represents an optionally substituted alkyl group or an optionally substituted aromatic ring group. The plurality of R groups included may be the same or different. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R1～R6In the case of the alkyl group, the number of carbon atoms and the number of substituents are the same. Examples of the preferable number of carbon atoms and optional substituents of the aromatic ring group are the same as those of the above-mentioned R1～R6In the case of the aromatic ring group, the number of carbon atoms and the number of substituents are the same.
Specific examples thereof include: and quaternary alkylammonium cations having 1 to 6 carbon atoms (e.g., tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, etc.).
In addition, M is+Cation speciesThe number of the compounds is limited to1, and a mixture of a plurality of the compounds may be used. In addition, a plurality of compounds may be mixed in one molecule, or a plurality of compounds may be mixed in the colored resin composition.
As M+In view of solubility in an organic solvent used in the colored resin composition, preferred examples of the (d) compound include a hydrogen ion, an alkali metal cation, a tertiary ammonium cation, and a quaternary ammonium cation, and more preferred examples of the (d) compound include a lithium cation, a sodium cation, an unsubstituted ammonium cation, and a tetrabutylammonium cation.
n represents an integer of 0 to 4.
The larger n is, the more the compound (IV) is substituted with a hydrophilic group sulfo group, the higher the heat resistance and light resistance thereof, and the lower the solubility of the compound (IV) in the hydrophobic liquid crystal, and therefore the higher the voltage holding ratio, but from the viewpoint of high solubility in the organic solvent used in the colored resin composition, n is preferably 0 to 2.
[ Compound represented by the formula (IV-1) ]
The compound (IV) in the present invention is preferably a compound represented by the following formula (IV-1) (hereinafter, may be referred to as "compound (IV-1)") in view of excellent color purity and transmittance of a pixel obtained when used for a color filter.
[ chemical formula 24]
Figure BDA0001544982900000271
(in the above-mentioned formula,
R51～R56each independently represents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent.
Adjacent R51～R56Or may be linked to each other to form a ring, which may have a substituent.
R57And R58Each independently represents a hydrogen atom or an optional substituent.
R57And R58Or may be linked to each other to form a ring, which may have a substituent.
The benzene ring and the indole ring in the formula (IV-1) may further have an optional substituent. )
SO represented by the above formula (IV-1)3 -The radicals are substituted on any carbon of the indole ring. Further, the benzene ring in the above formula (IV-1) and R described below11～R18In the case where the substituent(s) is a sulfo group, the sulfo group may be bonded to M shown in the above formula (IV)+A salt is formed.
(with respect to R)51～R56)
R51～R56Respectively with R in the compound (IV)41～R46The meaning is the same. The specific examples and preferred embodiments are also the same.
(with respect to R)57And R58)
R57And R58Respectively with R in the compound (IV)47And R48The meaning is the same. The specific examples and preferred embodiments are also the same.
[ Compound represented by the formula (IV-2) ]
The compound (IV) of the present invention is preferably a compound represented by the following formula (IV-2) (hereinafter, may be referred to as "compound (IV-2)") in view of excellent color purity and transmittance of a pixel obtained when used in a color filter.
[ chemical formula 25]
Figure BDA0001544982900000281
(in the above formula)
R61～R65Each independently represents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent.
Adjacent R61～R65Or may be linked to each other to form a ring, which may have a substituent.
R67And R68Each independently represents a hydrogen atom or an optional substituent.
R67And R68Or may be linked to each other to form a ring, which may have a substituent.
Q2Represents 1 group selected from the following group or a group in which 2 or more of these groups are bonded: a 2-valent aromatic ring group optionally having a substituent, a 2-valent aliphatic hydrocarbon group optionally having a substituent, a 2-valent aliphatic heterocyclic group optionally having a substituent, -C (═ O) -, -O-, -S-, -NH-.
The benzene ring and the indole ring in the formula (IV-2) may further have an optional substituent. )
Benzene ring, indole ring, Q in the above formula (IV-2)2R in the following description61～R65And R67And R68In the case where the substituent(s) is a sulfo group, the sulfo group may be bonded to M shown in the above formula (IV)+A salt is formed.
(with respect to R)61～R65)
R61～R65Respectively with R in the compound (IV)41～R45The meaning is the same. The specific examples and preferred embodiments are also the same.
(with respect to R)67And R68)
R67And R68Respectively with R in the compound (IV)47And R48The meaning is the same. The specific examples and preferred embodiments are also the same.
(with respect to Q)2)
Q2Represents 1 group selected from the following group or a group in which 2 or more of these groups are bonded: a 2-valent aromatic ring group optionally having a substituent, a 2-valent aliphatic hydrocarbon group optionally having a substituent, a 2-valent aliphatic heterocyclic group optionally having a substituent, -C (═ O) -, -O-, -S-, -NH-.
Examples of the 2-valent aromatic ring group include those described above (with respect to R)51～R56) The aromatic ring having 1 free valence described in the above item is a group having 2 to 14 carbon atoms and having 2 free valence aromatic rings. As the substituent optionally having on these groups, for example: above (substituent group W)2) The group of (1).
As the 2-valent fatThe aliphatic hydrocarbon group includes a linear, branched or cyclic aliphatic hydrocarbon group, and the number of carbon atoms thereof is usually 1 or more, usually 8 or less, and preferably 6 or less. Specific examples thereof include: an alkylene group having 1 to 8 carbon atoms, a cyclopentanediyl group, a cyclohexanediyl group, and the like. As the substituent optionally having on these groups, for example: above (substituent group W)2) The group of (1).
Examples of the 2-valent aliphatic heterocyclic group include: piperidinyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, piperazinyl, morpholinyl, indolyl, isoindolyl, and the like. As the substituent optionally having on these groups, for example: above (substituent group W)2) The group of (1).
[ Compound represented by the formula (IV-3) ]
The compound (IV) of the present invention is preferably a compound represented by the following formula (IV-3) (hereinafter, may be referred to as "the compound (IV-3) of the present invention") in view of excellent color purity and transmittance of a pixel obtained when used in a color filter.
[ chemical formula 26]
Figure BDA0001544982900000291
(in the above-mentioned formula,
R71～R73and R75～R76Each independently represents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent.
Q3Represents 1 group selected from the following group or a group in which 2 or more of these groups are bonded: a 2-valent aromatic ring group optionally having a substituent, a 2-valent aliphatic hydrocarbon group optionally having a substituent, a 2-valent aliphatic heterocyclic group optionally having a substituent, -C (═ O) -, -O-, -S-, -NH-.
Adjacent R71And R72、R73And Q3And R75And R76Or may be linked to each other to form a ring, which may have a substituent.
R77And R78Each independently represents a hydrogen atom or an optional substituent.
R77And R78Or may be linked to each other to form a ring, which may have a substituent.
The benzene ring and the indole ring in the formula (IV-3) may further have an optional substituent. )
Benzene ring, indole ring in the above formula (IV-3), Q described below3、R71～R75And R77～R78In the case where the substituent(s) is a sulfo group, the sulfo group may be bonded to M shown in the above formula (IV)+A salt is formed.
(with respect to R)71～R73、R75、R76)
R71～R73、R75、R76Respectively with R in the compound (IV)41～R43、R45、R46The meaning is the same. Specific examples and preferred embodiments are also the same.
(with respect to R)77And R78)
R77And R78Respectively with R in the compound (IV)47～R48The meaning is the same. Specific examples and preferred embodiments are also the same.
(with respect to Q)3)
Q3Represents 1 group selected from the following group or a group in which 2 or more of these groups are bonded: a 2-valent aromatic ring group optionally having a substituent, a 2-valent aliphatic hydrocarbon group optionally having a substituent, a 2-valent aliphatic heterocyclic group optionally having a substituent, -C (═ O) -, -O-, -S-, -NH-.
Examples of the 2-valent aromatic ring group include those described above (with respect to R)51～R56) The aromatic ring having 1 free valence described in the above item is a group having 2 to 14 carbon atoms and having 2 free valence aromatic rings. As the substituent optionally having on these groups, for example: above (substituent group W)2) The group of (1).
The 2-valent aliphatic hydrocarbon group includes a linear, branched or cyclic aliphatic hydrocarbon group, andthe number of carbon atoms is usually 1 or more, usually 8 or less, and preferably 6 or less. Specific examples thereof include: an alkylene group having 1 to 8 carbon atoms, a cyclopentanediyl group, a cyclohexanediyl group, and the like. As the substituent optionally having on these groups, for example: above (substituent group W)2) The group of (1).
Examples of the 2-valent aliphatic heterocyclic group include: piperidinyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, piperazinyl, morpholinyl, indolyl, isoindolyl, and the like. As the substituent optionally having on these groups, for example: above (substituent group W)2) The group of (1).
[ molecular weight ]
The molecular weight of the compound (IV) of the present invention is usually 500 or more, preferably 600 or more, and usually 5000 or less, preferably 2000 or less.
When the molecular weight of the compound (IV) is within the above range, the compound is preferable because the compound has good solubility in a solvent and can be easily produced.
Preferred specific examples of the compound (IV) of the present invention are shown below, but the present invention is not limited to these examples.
[ specific examples of the Compound (IV) of formula ]
[ chemical formula 27]
Figure BDA0001544982900000311
[ chemical formula 28]
Figure BDA0001544982900000321
[ chemical formula 29]
Figure BDA0001544982900000331
[ chemical formula 30]
Figure BDA0001544982900000341
[ chemical formula 31]
Figure BDA0001544982900000351
[ chemical formula 32]
Figure BDA0001544982900000361
[ chemical formula 33]
Figure BDA0001544982900000371
[ chemical formula 34]
Figure BDA0001544982900000381
[ chemical formula 35]
Figure BDA0001544982900000391
[ chemical formula 36]
Figure BDA0001544982900000401
[ chemical formula 37]
Figure BDA0001544982900000411
[ Synthesis method ]
The above-mentioned compounds (II) to (IV) can be synthesized, for example, by the methods described in j. chem.soc., perkintrans.1998,2,297, international publication No. 2006/120205, synthetic dye review (Gross-synthetic dye)' (horiba, published by mitsui, co-published 1968).
(triarylmethane dye: a compound represented by the formula (V))
[ chemical formula 38]
Figure BDA0001544982900000412
(in the formula (V), Rb1～Rb4Each independently represents a hydrogen atom, -Rb6Or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
Rb5represents-SO3 -、-SO3H、-SO3M、-CO2H、-CO2Rb6、-SO3Rb6、-SO2NHRb8or-SO2NRb8Rb9。
m represents an integer of 0 to 5. When m is an integer of 2 or more, plural Rb5May be the same or different.
Rb6Represents a saturated hydrocarbon group having 1 to 10 carbon atoms.
Rb8And Rb9Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms or-Q1.
Q1 represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms.
M represents a sodium atom or a potassium atom.
D represents a halogen atom. a represents an integer of 0 or 1. )
(with respect to R)b6)
As Rb6Examples thereof include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl, 2-ethylhexyl, cyclooctyl, nonyl, decyl, tricyclodecyl, methoxypropyl, ethoxypropyl, hexyloxypropyl, 2-ethylhexyloxypropyl, methoxyhexyl, ethoxypropyl and the like.
as-SO3Rb6Examples thereof include: methylsulfonyl, ethylsulfonyl, hexylsulfonyl, decylsulfonyl, and the like.
as-CO2Rb6Examples thereof include: methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, pentyloxycarbonyl, isopentyloxyAlkylcarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, cyclooctyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, tricyclodecyloxycarbonyl, methoxypropoxycarbonyl, ethoxypropoxycarbonyl, hexyloxypropoxycarbonyl, 2-ethylhexyloxypropoxycarbonyl, methoxyhexyloxycarbonyl and the like.
as-SO2NHRb8Examples thereof include: aminosulfonyl, methylaminosulfonyl, ethylaminosulfonyl, propylaminosulfonyl, isopropylaminosulfonyl, butylaminosulfonyl, isobutylaminosulfonyl, pentylaminosulfonyl, isopentylaminosulfonyl, neopentylaminosulfonyl, cyclopentylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, heptylaminosulfonyl, cycloheptylaminosulfonyl, octylaminosulfonyl, 2-ethylhexylaminosulfonyl, 1, 5-dimethylhexylaminosulfonyl, cyclooctylaminosulfonyl, nonylaminosulfonyl, decylaminosulfonyl, tricyclodecylaminosulfonyl, methoxypropylaminosulfonyl, ethoxypropylaminosulfonyl, propoxypropylaminosulfonyl, isopropoxypropylaminosulfonyl, hexyloxypropylaminosulfonyl, 2-ethylhexyloxypropylaminosulfonyl, tert-hexyloxysropylaminosulfonyl, tert-oxysulfonyl, sulfonylamino, and mixtures thereof, Methoxyhexylaminosulfonyl, 3-phenyl-1-methylpropylaminosulfonyl and the like.
as-SO2NHRb8and-SO2NRb8Rb9Further, a group represented by the following formula can be exemplified.
[ chemical formula 39]
Figure BDA0001544982900000431
[ chemical formula 40]
Figure BDA0001544982900000432
In the above formula, X1Represents a halogen atom. As X1Examples of the halogen atom in (2) include a fluorine atom, a chlorine atom and a bromine atom.
[ chemical formula 41]
Figure BDA0001544982900000441
[ chemical formula 42]
Figure BDA0001544982900000442
[ chemical formula 43]
Figure BDA0001544982900000443
[ chemical formula 44]
Figure BDA0001544982900000451
In the above formula, X3Represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, wherein hydrogen atoms of the alkyl group and the alkoxy group are optionally substituted by a halogen atom.
Examples of the alkyl group having 1 to 3 carbon atoms which is optionally substituted with a halogen atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a perfluoromethyl group.
Examples of the alkoxy group having 1 to 3 carbon atoms which is optionally substituted with a halogen atom include a methoxy group, an ethoxy group, and a propoxy group.
[ chemical formula 45]
Figure BDA0001544982900000452
[ chemical formula 46]
Figure BDA0001544982900000461
[ chemical formula 47]
Figure BDA0001544982900000462
[ chemical formula 48]
Figure BDA0001544982900000463
In the above formula, X2Represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and the hydrogen atoms of the alkyl group and the alkoxy group are optionally substituted by a halogen atom.
As X2Examples of the halogen atom in (2) include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 3 carbon atoms which is optionally substituted with a halogen atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a perfluoromethyl group.
Examples of the alkoxy group having 1 to 3 carbon atoms which is optionally substituted with a halogen atom include a methoxy group, an ethoxy group, and a propoxy group.
[ chemical formula 49]
Figure BDA0001544982900000471
[ chemical formula 50]
Figure BDA0001544982900000472
[ chemical formula 51]
Figure BDA0001544982900000473
[ chemical formula 52]
Figure BDA0001544982900000481
[ chemical formula 53]
Figure BDA0001544982900000482
In the above formula, X2The same meanings as described above are indicated.
[ chemical formula 54]
Figure BDA0001544982900000491
[ chemical formula 55]
Figure BDA0001544982900000492
[ chemical formula 56]
Figure BDA0001544982900000493
[ chemical formula 57]
Figure BDA0001544982900000501
In the above formula, X3The same meanings as described above are indicated.
as-SO2NRb8Rb9R contained in (1)b8And Rb9Preferably, a branched alkyl group having 6 to 8 carbon atoms, an alicyclic alkyl group having 5 to 7 carbon atoms, an allyl group, a phenyl group, an aralkyl group having 8 to 10 carbon atoms, a hydroxyalkyl group and an aryl group having 2 to 8 carbon atoms, or an alkoxyalkyl group or an aryl group having 2 to 8 carbon atoms, and particularly preferably a 2-ethylhexyl group.
Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.
As the C6-10 aromatic hydrocarbon substituents, preferably ethyl, propyl, phenyl, two methyl phenyl, -SO3Rb6or-SO2NHRb8. Examples of the halogen atom as a substituent of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom and the like.
As the C6-10 aromatic hydrocarbon substituents, preferably ethyl, propyl, phenyl, two methyl phenyl, -SO3Rb6or-SO2NHRb8。
The substituted aromatic hydrocarbon group having 6 to 10 carbon atoms includes: methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, hexylphenyl, decylphenyl, fluorophenyl, chlorophenyl, bromophenyl, hydroxyphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, decyloxyphenyl, trifluoromethylphenyl and the like.
(Synthesis method of Compound (V))
Compound (V) can be produced as follows: for example, the reaction of a compound having a-SO group is carried out by a conventional method3Chlorinating the pigment or pigment intermediate of H, and subjecting the resultant to have-SO2A pigment or a pigment intermediate of Cl and R8-NH2The amine represented by (a) is reacted to produce the compound (V). Further, the compound (V) can also be produced by chlorinating a dye produced by the method described in Japanese patent application laid-open No. 3-78702, page 3, upper right column to lower left column, in the same manner as described above, and then reacting the resulting product with an amine.
(specific examples)
Specific examples of the compound (V) are shown below.
[ chemical formula 58]
Figure BDA0001544982900000511
[ chemical formula 59]
Figure BDA0001544982900000521
[ chemical formula 60]
Figure BDA0001544982900000531
(cyanine dye: a compound represented by the formula (VI))
The cyanine dye is particularly preferably a compound represented by the following formula (VI) (hereinafter, may be referred to as "compound (VI)") in view of high heat resistance, light resistance and transmittance.
[ chemical formula 61]
Figure BDA0001544982900000541
(in the formula, Zm3-represents an m3 valent anion.
m3 represents an integer of 1 to 4.
Ar1And Ar2Each independently represents a nitrogen-containing heterocyclic group which may have a substituent.
q represents an integer of 1 to 5. )
(about q)
q represents an integer of 1 to 5.
In view of the heat resistance of the coloring material, q is preferably 1 to 5, and particularly preferably 1 to 3.
(with respect to Ar)1And Ar2)
Ar1And Ar2Each independently represents a nitrogen-containing heterocyclic group which may have a substituent.
Examples of the nitrogen-containing heterocyclic group include: having 1 free valence of an indole ring, a benzindole ring, an indolenine ring, a benzindoline ring,
Figure BDA0001544982900000542
Azolyl ring, benzo
Figure BDA0001544982900000543
An azole ring, a thiazole ring, a benzothiazole ring, a benzimidazole ring, a quinoline ring, etc. Among them, from the viewpoint of high luminance, an indole ring, a benzindole ring, an indolenine ring, and a benzindole ring are preferable, and an indole ring and a benzindole ring are more preferable.
In addition, as Ar1And Ar2The substituent (b) optionally contained in the nitrogen-containing heterocycle in (1) is not particularly limited insofar as the effect of the present invention is not impaired, and there may be mentioned:
aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, and tert-pentyl groups;
phenyl radicalO-tolyl group, m-tolyl group, p-tolyl group, xylyl group,
Figure BDA0001544982900000544
Aromatic hydrocarbon groups such as o-cumyl, m-cumyl and p-cumyl;
alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and pentyloxy;
aryloxy groups such as phenoxy group;
aralkyloxy such as benzyloxy;
groups having an ester bond such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, acetoxy, benzoyloxy and the like;
alkylaminosulfonyl groups such as methylaminosulfonyl, dimethylaminosulfonyl, ethylaminosulfonyl, diethylaminosulfonyl, n-propylaminosulfonyl, di-n-propylaminosulfonyl, isopropylaminosulfonyl, diisopropylaminosulfonyl, n-butylaminosulfonyl, and di-n-butylaminosulfonyl;
alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl and tert-butylsulfonyl;
a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.;
nitro and cyano.
When the substituent has a hydrogen atom, the hydrogen atom may be substituted with the following group: for example, a halogen atom such as a fluorine atom, chlorine atom, bromine atom, iodine atom, etc.; alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and pentyloxy; aryloxy groups such as phenoxy and benzyloxy; phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, m-tolyl,
Figure BDA0001544982900000552
O-cumyl, m-cumyl, p-cumyl and the likeAn aromatic hydrocarbon group; a carboxyl group; a cyano group; a nitro group; and so on.
The compound represented by the formula (VI) may have any isomer, as long as it has a cis-trans isomer in the cationic site.
The compound represented by the above formula (VI) is more preferably a compound represented by the following formula (VI-1) from the viewpoint of improving the brightness and heat resistance of the coating film.
[ chemical formula 62]
Figure BDA0001544982900000551
(in the formula (VI-1), n is as defined above for the formula (VI).
R901And R902Each independently represents an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms.
R91And R92Each independently represents-O-, -S-, -N-, -Se-or-CR903R904-。
R903And R904Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
In addition, R is91And R92is-CR903R904In the case of-R903The rings may be bonded to each other to form a ring. The ring optionally has a substituent.
Ring Y1And Y2Each independently represents a benzene ring optionally having a substituent, or a naphthalene ring optionally having a substituent.
R81And R82Each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent.
In addition, R is81And R82The ring may be bonded to each other to form a ring. )
(with respect to R)901And R902)
R901And R902Each independently representsAn optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms.
Examples of the aliphatic hydrocarbon group include: methyl, ethyl, ethenyl, ethynyl, propyl, isopropyl, isopropenyl, 1-propenyl, 2-propynyl, butyl, isobutyl, sec-butyl, tert-butyl, 2-butenyl, 1, 3-butadienyl, pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylpentyl, 2-penten-4-ynyl, hexyl, isohexyl, 5-methylhexyl, heptyl, octyl.
Examples of the substituent optionally contained in the aliphatic hydrocarbon group include: phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, m-tolyl,
Figure BDA0001544982900000561
Aromatic hydrocarbon groups such as o-cumyl, m-cumyl and p-cumyl;
alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, phenoxy, and benzyloxy;
a halogenated group such as a fluoro group, a chloro group, a bromo group, an iodo group, etc.;
and carboxyl, nitro, cyano.
R901And R902Each preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.
(with respect to R)91And R92)
R91And R92Each independently represents-O-, -S-, -N-, -Se-or-CR903R904-。
R903And R904Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
Wherein R is91And R92is-CR903R904In the case of-R903And optionally bonded to each other to form a ring.
As a group consisting of R91And R92Optionally rings bonded to each otherExamples of preferable specific examples of (a) include the following rings, but the present invention is not limited to these examples.
[ chemical formula 63]
Figure BDA0001544982900000571
(about Ring Y)1And Y2)
Ring Y1And Y2Each independently represents a benzene ring optionally having a substituent, or a naphthalene ring optionally having a substituent.
As R903And R904Of (5) an aliphatic hydrocarbon group consisting of R91And R92Optionally bonded to each other to form a ring, and ring Y1And Y2Wherein the benzene ring and the naphthalene ring optionally have a substituent, the above-mentioned R is mentioned901And R902The aliphatic hydrocarbon group in (1) optionally has a substituent.
(with respect to R)81And R82)
R81And R82Each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent.
In addition, R is81And R82The ring may be bonded to each other to form a ring.
R81And R82With R in the above formula (II-1)21And R22The same meaning, and the same preferred form.
That is, the anion in the compound represented by the formula (VI-1) is more preferably a compound represented by the formula (II '-1) or (II' -2).
In addition, the compound represented by the above formula (VI) may be represented by, for example, R901～R902And R91And R92The linking group is extended to form a dimer, trimer, etc.
Preferred specific examples of the compound represented by the formula (VI) in the present invention will be shown below, but the present invention is not limited to these examples.
[ specific examples ]
[ chemical formula 64]
Figure BDA0001544982900000581
When the colored resin composition of the present invention is a red pixel-forming colored resin composition or a green pixel-forming colored resin composition, a yellow dye may be used as a complementary color.
In the case of including a yellow dye, there is also a tendency that: until the solvent resistance is lowered, the image formability and the developability are insufficient.
The reason for this is presumed to be: since the absorption wavelength of the yellow dye and the absorption wavelength of the photopolymerization initiator overlap each other, the photopolymerization initiator cannot sufficiently obtain light energy, and thus the amount of radicals generated decreases, and the photopolymerization initiator contained in the colored resin composition cannot sufficiently function.
That is, when the yellow dye described later is contained in the colored resin composition, the effect of the present invention is more easily obtained, and therefore, it is preferable.
The yellow dye will be described in detail below.
[ yellow dye ]
Examples of the yellow dye in the present invention include: azo dyes, quinophthalone dyes, cyanine dyes, anthraquinone dyes, methine dyes, dipyrromethene dyes, and the like, and among them, azo dyes are preferable.
Examples of the azo dyes include: pyridone azo dyes, pyrazolone azo dyes, barbituric acid azo dyes, and the like, and particularly, pyridone azo dyes are preferable because they have a sharp absorption edge at 400nm to 500nm in the absorption spectrum and can give a pixel having high brightness.
The pyridone azo dye is not particularly limited, and a known one can be used, but a compound represented by the following formula (VII) (hereinafter, may be referred to as "compound (VII)") is preferable in view of high solubility in the colored resin composition.
[ chemical formula 65]
Figure BDA0001544982900000591
(in the above formula (VII), A represents an optionally substituted aromatic hydrocarbon ring group or an optionally substituted heterocyclic group.
R1aRepresents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a carboxyl group or a trifluoromethyl group.
R2aRepresents a hydrogen atom, a cyano group, a carbamoyl group, an alkylcarbamoyl group which may be substituted, an arylcarbamoyl group which may be substituted, a carboxyl group, an aminosulfonyl group or a sulfo group.
R3aRepresents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an aralkyl group having 7 to 20 carbon atoms which may be substituted, a heterocyclic group having 3 to 20 carbon atoms which may be substituted, a carbamoyl group, an alkylcarbamoyl group having 2 to 20 carbon atoms which may be substituted, an arylcarbamoyl group having 7 to 30 carbon atoms which may be substituted, a sulfamoyl group, an alkylaminosulfonyl group having 1 to 20 carbon atoms which may be substituted, an arylaminosulfonyl group having 6 to 30 carbon atoms which may be substituted, an alkoxycarbonyl group having 2 to 20 carbon atoms which may be substituted, an aryloxycarbonyl group having 7 to 30 carbon atoms which may be substituted, an acyl group having 2 to 30 carbon atoms which may be substituted, an alkylsulfonyl group having 1 to 30 carbon atoms which may be substituted, an alkoxycarbonylyl group having 2 to 20 carbon atoms which may be substituted, an alkoxycarbonylyl group having 2 to 30 carbon atoms which may be substituted, an, Or an arylsulfonyl group having 6 to 30 carbon atoms and optionally having a substituent. )
(about A)
A represents an optionally substituted aromatic hydrocarbon ring group or an optionally substituted heterocyclic group.
Examples of the aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, perylene,
Figure BDA0001544982900000601
A ring, a benzophenanthrene ring, an acenaphthylene ring, a benzoacenaphthylene ring, a fluorene ring, etc.
Examples of the heterocyclic group include: pyrrolyl, imidazolyl, pyrazolyl, thiazolyl,
Figure BDA0001544982900000602
Oxazolyl, triazolyl, thiadiazolyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, benzothiazolinyl, phthalimidyl, benzimidazolonyl, furyl, thienyl, and the like.
The aromatic hydrocarbon ring group or the heterocyclic group may optionally have a substituent, and is preferably a hydrophilic group in view of improving the solubility of the compound (I) in a solvent, or a group having an electron donating property or an electron withdrawing property in view of enabling the color tone to be adjusted.
More specifically, there may be mentioned: an alkyl group optionally having a substituent, an aryl group optionally having a substituent, a 1-valent heterocyclic group optionally having a substituent, an alkoxy group optionally having a substituent, an amino group, an alkylamino group optionally having a substituent, an arylamino group optionally having a substituent, an acylamino group optionally having a substituent, a carbamoyl group, an alkylcarbamoyl group optionally having a substituent, an arylcarbamoyl group optionally having a substituent, a sulfamoyl group, an alkylaminosulfonyl group optionally having a substituent, an arylaminosulfonyl group optionally having a substituent, an alkoxycarbonyl group optionally having a substituent, an aryloxycarbonyl group optionally having a substituent, a nitro group, a carboxyl group, a sulfo group, a hydroxyl group, a cyano group, a halogen atom and the like.
The number of carbon atoms of the alkyl group which may have a substituent is usually 1 or more, and usually 12 or less, preferably 10 or less. As the group optionally substituted on the alkyl group, there can be exemplified: alkoxy group having 1 to 10 carbon atoms, phenyl group, hydroxyl group, amino group, dimethylamino group, diethylamino group, halogen atom, cyano group, sulfo group, carboxyl group, and the like. Specific examples of the alkyl group include: methyl, ethyl, n-propyl, hydroxyethyl, 1, 2-dihydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2- (2-methoxyethoxy) ethyl, 2- (2-ethoxyethoxy) ethyl, 2- (2-butoxyethoxy) ethyl, benzyl, phenethyl and the like.
The number of carbon atoms of the aryl group which may have a substituent is usually 6 or more, and usually 14 or less, preferably 12 or less. Examples of the aryl group include: phenyl, naphthyl, anthracenyl, and the like. As the group optionally substituted on the aryl group, there can be exemplified: alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, hydroxyl group, amino group, dimethylamino group, diethylamino group, halogen atom, sulfo group, carboxyl group and the like. Specific examples of the aryl group include: phenyl, p-tolyl, m-tolyl, p-methoxyphenyl, naphthyl, anthryl, and the like.
The number of carbon atoms of the 1-valent heterocyclic group which may have a substituent is usually 2 or more, and usually 14 or less, preferably 12 or less. Examples of the 1-valent heterocyclic group include: pyrrolyl, imidazolyl, pyrazolyl, thiazolyl,
Figure BDA0001544982900000611
Oxazolyl, triazolyl, thiadiazolyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, benzothiazolinyl, phthalimidyl, benzimidazolonyl, furyl, thienyl, pyranyl, piperidinyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, piperazinyl, morpholinyl, indolyl, isoindolyl and the like. As the group optionally substituted on the 1-valent heterocyclic group, there can be mentioned: alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, hydroxyl group, amino group, dimethylamino group, diethylamino group, halogen atom, sulfo group, carboxyl group and the like. Specific examples of the 1-valent heterocyclic group include: 2-pyrrolyl, 2-imidazolyl, 1-pyrazolyl, 2-thiazolyl, 2-
Figure BDA0001544982900000612
Azolyl, 1,2, 4-triazol-1-yl, 4-pyridyl, 2-pyrimidyl, 4, 6-diamino-2-triazinyl, 8-quinolyl, 8-isoquinolyl, 2-benzothiazolinyl, 6-methyl-7-thio-2-benzothiazolinyl1, 3-dihydro-1, 3-dioxo-2H-isoindol-2-yl, 1H-benzimidazol-2-yl, 2-furyl, 2-thienyl, 1-piperidyl, 1-pyrrolidinyl, 1-imidazolidinyl, 1-pyrazolidinyl, 1-piperazinyl, 1-morpholinyl, 1-indolyl, 2-isoindolyl.
The number of carbon atoms of the alkoxy group which may have a substituent is usually not less than 1, and usually not more than 12, preferably not more than 10. As the group optionally substituted on the alkoxy group, there may be mentioned: alkoxy group having 1 to 10 carbon atoms, phenyl group, hydroxyl group, amino group, dimethylamino group, diethylamino group, halogen atom, cyano group, sulfo group, carboxyl group, and the like. Specific examples of the alkoxy group include: methoxy, ethoxy, n-propoxy, n-butoxy, hydroxyethoxy, 1, 2-dihydroxypropoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2- (2-methoxyethoxy) ethoxy, 2- (2-ethoxyethoxy) ethoxy, 2- (2-butoxyethoxy) ethoxy, benzyloxy, phenethyloxy and the like.
Alkylamino optionally having a substituent group or-NR11aR12aIs represented by R11aRepresents an optionally substituted alkyl group, R12aRepresents a hydrogen atom or an alkyl group optionally having a substituent. The alkyl group has usually 1 or more carbon atoms, usually 12 or less, and preferably 10 or less. As the group optionally substituted on the alkyl group, there can be exemplified: alkoxy group having 1 to 10 carbon atoms, phenyl group, hydroxyl group, amino group, dimethylamino group, diethylamino group, halogen atom, cyano group, sulfo group, carboxyl group, and the like. Specific examples of the alkyl group include: methyl, ethyl, n-propyl, n-butyl, cyclohexyl, hydroxyethyl, 1, 2-dihydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2- (2-methoxyethoxy) ethyl, 2- (2-ethoxyethoxy) ethyl, 2- (2-butoxyethoxy) ethyl, benzyl, phenethyl and the like. Specific examples of the alkylamino group include: ethylamino, dimethylamino, diethylamino, dibutylamino, bis (2-ethoxyethyl) amino, diphenylethylethylamino, cyclohexylethyl and the like.
Arylamino optionally having substituents with-NR13aR14aIs represented by R13aRepresents an optionally substituted aryl group, R14aRepresents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R11aAnd R12aThe substituents optionally having on the alkyl group of (1) are the same. The aryl group has usually 6 or more carbon atoms, usually 14 or less, preferably 12 or less, and includes a phenyl group, a naphthyl group, an anthracenyl group and the like. As the group optionally substituted on the aryl group, there can be exemplified: an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, and the like. Specific examples of the aryl group include: phenyl, p-tolyl, m-tolyl, p-methoxyphenyl, naphthyl, anthryl, and the like. Specific examples of the arylamino group include: phenylamino, diphenylamino, di (p-tolyl) amino, di (p-methoxyphenyl) amino, ethylphenylamino, n-butylphenylamino and the like.
Acylamino optionally having substituent(s) by-NH-COR15aIs represented by R15aRepresents an optionally substituted alkyl group, an optionally substituted aryl group. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R11aAnd R12aIn the case of the alkyl group, the number of carbon atoms and the number of substituents are the same. Examples of the preferable number of carbon atoms and optional substituents of the aryl group are the same as those of the above-mentioned R13aThe substituents optionally having on the aryl group of (1) are the same. Specific examples of acylamino groups include: acetylamino, benzoylamino, 2-ethylhexanoylamino and the like.
Alkylcarbamoyl optionally having substituent(s) -CO-NR16aR17aIs represented by R16aAnd R17aEach independently represents a hydrogen atom or an alkyl group optionally having a substituent. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R11aAnd R12aThe substituents optionally having on the alkyl group of (1) are the same. Specific examples of the alkylcarbamoyl group include: methylcarbamoyl, ethylCarbamoyl, phenethylcarbamoyl, 2-ethylhexylcarbamoyl, 2-ethoxyethylcarbamoyl, 2- (2-ethoxyethoxy) ethylcarbamoyl and the like.
Arylcarbamoyl optionally having substituent(s) -CO-NR18aR19aIs represented by R18aRepresents an optionally substituted aryl group. R19aRepresents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R11aAnd R12aThe substituents optionally having on the alkyl group of (1) are the same. Examples of the preferable number of carbon atoms and optional substituents of the aryl group are the same as those of the above-mentioned R13aIn the case of the aryl group, the number of carbon atoms and the number of substituents are the same. Specific examples of the arylcarbamoyl group include: phenylcarbamoyl, naphthylcarbamoyl, p-tolylcarbamoyl, p-methoxyphenylcarbamoyl and the like.
Alkylaminosulfonyl optionally having substituent(s) and-SO2-NR20aR21aIs represented by R20aAnd R21aEach independently represents a hydrogen atom or an alkyl group optionally having a substituent. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R11aAnd R12aThe substituents optionally having on the alkyl group of (1) are the same. Specific examples of the alkylaminosulfonyl group include: methylaminosulfonyl, ethylaminosulfonyl, phenethylaminosulfonyl, 2-ethylhexylaminosulfonyl, 2-ethoxyethylaminosulfonyl, 2- (2-ethoxyethoxy) ethylaminosulfonyl and the like.
Arylaminosulfonyl optionally having substituents and-SO2-NR22aR23aIs represented by R22aRepresents an optionally substituted aryl group. R23aRepresents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R11aAnd R12aThe substituents optionally having on the alkyl group of (1) are the same. Preferred carbon atom of the aryl groupExamples of the number of subgroups, optional substituents and the above-mentioned R13aIn the case of the aryl group, the number of carbon atoms and the number of substituents are the same. Specific examples of the arylaminosulfonyl group include: phenylaminosulfonyl, naphthylaminosulfonyl, p-tolylaminosulfonyl, p-methoxyphenylaminosulfonyl and the like.
Alkoxycarbonyl optionally having substituent(s) by-CO-OR24aIs represented by R24aRepresents an alkyl group optionally having a substituent. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R11aAnd R12aThe substituents optionally having on the alkyl group of (1) are the same. Specific examples of the alkoxycarbonyl group include: methoxycarbonyl, ethoxycarbonyl, phenethyloxycarbonyl, 2-ethylhexyloxycarbonyl, 2-ethoxyethoxycarbonyl, 2- (2-ethoxyethoxy) ethoxycarbonyl and the like.
Aryloxy carbonyl optionally having substituent(s) represented by the formula-CO-OR25aIs represented by R25aRepresents an optionally substituted aryl group. Examples of the preferable number of carbon atoms and optional substituents of the aryl group are the same as those of the above-mentioned R23aThe substituents optionally having on the aryl group of (1) are the same. Specific examples of the aryloxycarbonyl group include: phenoxycarbonyl, naphthyloxycarbonyl, p-tolyloxycarbonyl, p-methoxyphenoxycarbonyl and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a fluorine atom and a chlorine atom having a high electronegativity are preferable.
(with respect to R)1a)
R1aRepresents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a carboxyl group or a trifluoromethyl group.
The number of carbon atoms of the alkyl group which may have a substituent is usually not less than 1, and usually not more than 10, preferably not more than 5. As the group optionally substituted on the alkyl group, there can be exemplified: alkoxy group having 1 to 8 carbon atoms, hydroxyl group, and the like. Specific examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, hydroxyethyl, methoxymethyl, and the like.
(aboutR2a)
R2aRepresents a hydrogen atom, a cyano group, a carbamoyl group, an alkylcarbamoyl group which may be substituted, an arylcarbamoyl group which may be substituted, a carboxyl group, an aminosulfonyl group or a sulfo group.
Alkylcarbamoyl optionally having substituent(s) -CO-NR56aR57aIs represented by R56aAnd R57aEach independently represents a hydrogen atom or an alkyl group optionally having a substituent. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R11aAnd R12aThe substituents optionally having on the alkyl group of (1) are the same. Specific examples of the alkylcarbamoyl group include: methylcarbamoyl, ethylcarbamoyl, phenethylcarbamoyl, 2-ethylhexylcarbamoyl, 2-ethoxyethylcarbamoyl, 2- (2-ethoxyethoxy) ethylcarbamoyl and the like.
Arylcarbamoyl optionally having substituent(s) -CO-NR58aR59aIs represented by R58aRepresents an optionally substituted aryl group. R59aRepresents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R11aAnd R12aThe substituents optionally having on the alkyl group of (1) are the same. Examples of the preferable number of carbon atoms and optional substituents of the aryl group are the same as those of the above-mentioned R13aIn the case of the aryl group, the number of carbon atoms and the number of substituents are the same. Specific examples of the arylcarbamoyl group include: phenylcarbamoyl, naphthylcarbamoyl, p-tolylcarbamoyl, p-methoxyphenylcarbamoyl and the like.
(with respect to R)3a)
R3aRepresents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an aralkyl group having 7 to 20 carbon atoms which may be substituted, a heterocyclic group having 3 to 20 carbon atoms which may be substituted, a carbamoyl group, a heterocyclic group having 2 carbon atoms which may be substituted20 is an alkylcarbamoyl group, an arylcarbamoyl group having 7 to 30 carbon atoms which may be substituted, an aminosulfonyl group, an alkylaminosulfonyl group having 1 to 20 carbon atoms which may be substituted, an arylaminosulfonyl group having 6 to 30 carbon atoms which may be substituted, an alkoxycarbonyl group having 2 to 20 carbon atoms which may be substituted, an aryloxycarbonyl group having 7 to 30 carbon atoms which may be substituted, an acyl group having 2 to 30 carbon atoms which may be substituted, an alkylsulfonyl group having 1 to 30 carbon atoms which may be substituted, or an arylsulfonyl group having 6 to 30 carbon atoms which may be substituted.
The number of carbon atoms of the alkyl group having 1 to 20 carbon atoms which may have a substituent is usually 1 or more, usually 20 or less, and preferably 15 or less. As the group optionally substituted on the alkyl group, there can be exemplified: alkoxy group having 1 to 15 carbon atoms, hydroxyl group, amino group, dimethylamino group, diethylamino group, halogen atom, cyano group, sulfo group, carboxyl group, and the like. Specific examples of the alkyl group include: methyl, ethyl, n-propyl, hydroxyethyl, 1, 2-dihydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2- (2-methoxyethoxy) ethyl, 2- (2-ethoxyethoxy) ethyl, 2- (2-butoxyethoxy) ethyl and the like.
The number of carbon atoms of the aryl group having 6 to 30 carbon atoms which may have a substituent is usually 6 or more, and usually 30 or less, preferably 25 or less. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group. As the group optionally substituted on the aryl group, there can be exemplified: an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a sulfo group, a carboxyl group, and the like. Specific examples of the aryl group include: phenyl, p-tolyl, m-tolyl, p-methoxyphenyl, naphthyl, anthryl, and the like.
The aralkyl group having 7 to 20 carbon atoms which may be optionally substituted has usually 7 or more carbon atoms, usually 20 or less carbon atoms, preferably 15 or less carbon atoms, and examples of the group optionally substituted on the aralkyl group include an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a sulfo group, a carboxyl group and the like, and specific examples of the aryl group include a benzyl group, a phenethyl group, an α -methylbenzyl group, a α -methylphenylethyl group, a β -methylphenylethyl group, a fluorenyl group and the like.
The number of carbon atoms of the heterocyclic group having 3 to 20 carbon atoms which may have a substituent is usually 3 or more, usually 20 or less, and preferably 15 or less. Examples of the 1-valent heterocyclic group include: pyrrolyl, imidazolyl, pyrazolyl, thiazolyl,
Figure BDA0001544982900000651
Oxazolyl, triazolyl, thiadiazolyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, benzothiazolinyl, phthalimidyl, benzimidazolonyl, furyl, thienyl, and the like. As the group optionally substituted on the 1-valent heterocyclic group, there can be mentioned: an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a sulfo group, a carboxyl group, and the like. Specific examples of the 1-valent heterocyclic group include: 2-pyrrolyl, 2-imidazolyl, 1-pyrazolyl, 2-thiazolyl, 2-
Figure BDA0001544982900000652
Azolyl, 1,2, 4-triazol-1-yl, 4-pyridyl, 2-pyrimidyl, 4, 6-diamino-2-triazinyl, 8-quinolyl, 8-isoquinolyl, 2-benzothiazolinyl, 6-methyl-7-thio-2-benzothiazolinyl, 1, 3-dihydro-1, 3-dioxo-2H-isoindol-2-yl, 1H-benzimidazol-2-yl, 2-furyl, 2-thienyl.
An optionally substituted alkylcarbamoyl group having 2 to 20 carbon atoms and a group-CO-NR60aR61aIs represented by R60aAnd R61aEach independently represents a hydrogen atom or an alkyl group optionally having a substituent. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R11aAnd R12aIn the case of the alkyl group, the number of carbon atoms and the number of substituents are the same. Specific examples of the alkylcarbamoyl group include: methylcarbamoyl, ethylcarbamoyl, phenethylcarbamoyl2-ethylhexylcarbamoyl group, 2-ethoxyethylcarbamoyl group, 2- (2-ethoxyethoxy) ethylcarbamoyl group and the like.
An optionally substituted arylcarbamoyl group having 7 to 30 carbon atoms and a-CO-NR group62aR63aIs represented by R62aRepresents an optionally substituted aryl group. R63aRepresents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R11aAnd R12aThe substituents optionally having on the alkyl group of (1) are the same. Examples of the preferable number of carbon atoms and optional substituents of the aryl group are the same as those of the above-mentioned R13aIn the case of the aryl group, the number of carbon atoms and the number of substituents are the same. Specific examples of the arylcarbamoyl group include: phenylcarbamoyl, naphthylcarbamoyl, p-tolylcarbamoyl, p-methoxyphenylcarbamoyl and the like.
An optionally substituted alkylaminosulfonyl group having 1 to 20 carbon atoms and-SO2-NR64aR65aIs represented by R64aAnd R65aEach independently represents a hydrogen atom or an alkyl group optionally having a substituent. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R11aAnd R12aThe substituents optionally having on the alkyl group of (1) are the same. Specific examples of the alkylsulfonamide group include: methylaminosulfonyl, ethylaminosulfonyl, phenethylaminosulfonyl, 2-ethylhexylaminosulfonyl, 2-ethoxyethylaminosulfonyl, 2- (2-ethoxyethoxy) ethylaminosulfonyl and the like.
An arylaminosulfonyl group having 6 to 30 carbon atoms and optionally having a substituent, and a compound represented by the formula-SO2-NR66aR67aIs represented by R66aRepresents an optionally substituted aryl group. R67aRepresents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R11aAnd R12aThe substituents optionally having on the alkyl group of (1) are the same. TheExamples of the preferable number of carbon atoms and optional substituents of the aryl group are the same as those of the above-mentioned R13aIn the case of the aryl group, the number of carbon atoms and the number of substituents are the same. Specific examples of the arylaminosulfonyl group include: phenylaminosulfonyl, naphthylaminosulfonyl, p-tolylaminosulfonyl, p-methoxyphenylaminosulfonyl and the like.
An alkoxycarbonyl group having 2 to 20 carbon atoms optionally having a substituent, and a group represented by the formula-CO-OR68aIs represented by R68aRepresents an alkyl group optionally having a substituent. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R11aAnd R12aThe substituents optionally having on the alkyl group of (1) are the same. Specific examples of the alkoxycarbonyl group include: methoxycarbonyl, ethoxycarbonyl, phenethyloxycarbonyl, 2-ethylhexyloxycarbonyl, 2-ethoxyethoxycarbonyl, 2- (2-ethoxyethoxy) ethoxycarbonyl and the like.
An optionally substituted aryloxycarbonyl group having 7 to 30 carbon atoms as a-CO-OR group69aIs represented by R69aRepresents an optionally substituted aryl group. Examples of the preferable number of carbon atoms and optional substituents of the aryl group are the same as those of the above-mentioned R23aThe substituents optionally having on the aryl group of (1) are the same. Specific examples of the aryloxycarbonyl group include: phenoxycarbonyl, naphthyloxycarbonyl, p-tolyloxycarbonyl, p-methoxyphenoxycarbonyl and the like.
An optionally substituted acyl group having 2 to 30 carbon atoms and-COR70aIs represented by R70aRepresents an optionally substituted alkyl group, an optionally substituted aryl group. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R11aAnd R12aThe substituents optionally having on the alkyl group of (1) are the same. Examples of the preferable number of carbon atoms and optional substituents of the aryl group are the same as those of the above-mentioned R13aIn the case of the aryl group, the number of carbon atoms and the number of substituents are the same. Specific examples of the acyl group include: acetyl, benzoyl, 2-ethylhexylcarbonyl, and the like.
An alkylsulfonyl group having 1 to 30 carbon atoms optionally having a substituentwith-SO2-R71aIs represented by R71aRepresents an alkyl group optionally having a substituent. Examples of the preferable number of carbon atoms and optional substituents of the alkyl group are the same as those of the above-mentioned R11aAnd R12aThe substituents optionally having on the alkyl group of (1) are the same. Specific examples of the alkylsulfonyl group include: methylsulfonyl, ethylsulfonyl, phenethylsulfonyl, 2-ethylhexylsulfonyl, 2-ethoxyethylsulfonyl, 2- (2-ethoxyethoxy) ethylsulfonyl and the like.
An arylsulfonyl group having 6 to 30 carbon atoms and optionally having a substituent, and a substituent represented by the formula-SO2-R72aIs represented by R72aRepresents an optionally substituted aryl group. Examples of the preferable number of carbon atoms and optional substituents of the aryl group are the same as those of the above-mentioned R23aThe substituents optionally having on the aryl group of (1) are the same. Specific examples of the arylsulfonyl group include: phenylsulfonyl, naphthylsulfonyl, p-tolylsulfonyl, p-methoxyphenylsulfonyl and the like.
[ specific examples of the compound of formula (VII) ]
Preferred specific examples of the compound (VII) are shown below, but the present invention is not limited to these examples.
[ chemical formula 66]
Figure BDA0001544982900000681
[ chemical formula 67]
Figure BDA0001544982900000691
In addition to the above structures, there can be enumerated: pyridone azo dyes described in each of Japanese patent application laid-open Nos. 2002-14223, 2005-126529, 2005-226022, 2006-58701, 2006-124634, 2009-280691, 2009-299030, 2010-1469, 2010-152160, 2010-168531, 2010-275533, 2011-148989, 2011-148990, 2011-148991, pyridone azo dyes described in each of Japanese patent application laid-open Nos. 2011-148990, dimerized pyridone azo dyes described in each of Japanese patent application laid-open Nos. 2011-148992, 2011-148993, dimerized pyridone azo dyes described in Japanese patent application laid-open Nos. 2010-265495, and polymerized pyridone azo dyes described in Japanese patent application laid-open Nos. 2010-open No. 170070731.
[ other color materials ]
The colored resin composition of the present invention contains the dye (a) as a coloring material, and other coloring materials may be used in combination in addition to the dye.
Examples of the other color materials include pigments, and they may be used in combination as appropriate according to the desired pixel color.
For example, when a blue pixel is to be formed, in the case where the dye contains the compound (II) or (VI), a violet pigment is suitably used as the pigment which can be used in combination.
As the violet pigment, there can be mentioned: c.i. pigment violet 1, 1:1, 2:2, 3:1, 3:3, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc. Among these pigments, c.i. pigment violet 19 and 23 are preferable, and c.i. pigment violet 23 is more preferable.
When the dye includes the compounds (III) to (V) in order to form a blue pixel, a blue pigment is preferably used as the pigment that can be used in combination.
Examples of the blue pigment include: c.i. pigment blue 1, 1:2, 9, 14, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56:1, 60, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc.
Among these pigments, a blue phthalocyanine copper pigment is preferable, and the phthalocyanine copper pigment includes c.i. pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 and the like, and further preferably c.i. pigment blue 15: 6.
When a green pixel is to be formed, if the dye contains the compound (VII), the green pixel is preferably used as a pigment which can be used in combination.
As the green pigment, there can be mentioned: c.i. pigment green 1,2,4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, etc. Among these pigments, c.i. pigment green 7, 36, 58 and the like are preferable.
In particular, c.i. pigment green 58 is preferable because the effects of the present invention can be easily obtained.
Further, a yellow pigment, a red pigment, and the like may be appropriately contained. As these pigments, for example, those described in Japanese patent laid-open publication No. 2009-25813 can be used.
When the coloring material contains a pigment, the average primary particle size of the pigment is usually 100nm or less, preferably 80nm or less, and more preferably 20nm or more and 70nm or less. In the present invention, the use of a composition containing a highly micronized pigment is particularly effective, and therefore the case where a pigment having an average primary particle size of 20nm or more and 60nm or less is contained is particularly preferable.
When the average primary particle size of the pigment used is within the above range, a pigment dispersion and a colored resin composition can be obtained which have good depolarization characteristics, can realize high contrast, high transmittance, and the like, and have good dispersion stability and excellent heat resistance and light resistance.
The primary particle size of the pigment can be determined by the following method.
First, a pigment was ultrasonically dispersed in chloroform, dropped on a mesh to which a collodion film was attached, dried, and observed by a Transmission Electron Microscope (TEM) to obtain a primary particle image of the pigment. In the case of an organic pigment, the particle diameter of each pigment particle is defined as an area equivalent circle diameter converted to the diameter of a circle having the same area, and the particle diameters are determined for a plurality of (usually about 200 to 300) pigment particles. The number average value was calculated by the following calculation formula using the obtained value of the primary particle diameter, and the average particle diameter was obtained.
[ mathematical formula 1]
Particle diameter of each pigment particle: x1，X2，X3，X4，····，Xi，······Xm
Figure BDA0001544982900000711
The pigment thus obtained may be used alone, but 1 or 2 or more pigments may be mixed and used within a range not impairing the effects of the present invention.
(content of color Material)
The content of the coloring material contained in the colored resin composition of the present invention varies depending on the desired pixel color, and for example, the total content of the dye (a) and the other coloring material is usually 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, and usually 50% by weight or less, more preferably 40% by weight or less, more preferably 30% by weight or less, based on the total solid content.
When the thickness is within the above range, the film thickness is moderate relative to the color density, and the gap control is easy when a liquid crystal cell is produced. Further, it is preferable because the dispersion stability is high and re-aggregation, thickening, and the like are less likely to occur.
[ (B) solvent ]
The solvent (B) in the present invention has a function of dissolving or dispersing each component contained in the colored resin composition to adjust the viscosity.
The solvent (B) may be any solvent capable of dissolving or dispersing the components constituting the colored resin composition, and is preferably selected to have a boiling point in the range of 100 to 200 ℃. More preferably a solvent having a boiling point of 120 to 170 ℃.
Examples of such a solvent include the following solvents.
Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethyl pentanol, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, and tripropylene glycol monomethyl ether;
glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether;
glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxyamyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;
ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether and dihexyl ether;
ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, and methyl nonyl ketone;
1-or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;
alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl;
aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;
linear or cyclic esters such as amyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ -butyrolactone;
alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
halogenated hydrocarbons such as chlorobutane and chloropentane;
ether ketones such as methoxymethylpentanone;
nitriles such as acetonitrile and benzonitrile:
examples of commercially available solvents that correspond to the above solvents include: mineral spirits (Mineral spirits), Varsol #2, Apco #18solvent, Apco thin, sonal solvent nos. 1 and 2, Solvesso #150, shellt ts28solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether (diglyme) (all of which are trade names of the above) and the like.
The solvent can be used alone in 1, also can be used in 2 or more combination.
Among the solvents, glycol monoalkyl ethers are preferred in view of the solubility of the dye (A) of the present invention. Among these, propylene glycol monomethyl ether is particularly preferable in view of the solubility of various components in the composition.
Further, for example, in the case where a pigment described later is contained as an optional component, it is more preferable to further use a glycol alkyl ether acetate as a solvent because a good balance of coatability, surface tension, and the like can be obtained and the solubility of the constituent components in the composition is high. In the composition containing a pigment, the diol monoalkyl ether has a high polarity and tends to aggregate the pigment, and therefore the viscosity of the colored resin composition may increase to lower the storage stability. Therefore, the amount of the glycol monoalkyl ethers used is preferably not too large, and the proportion of the glycol monoalkyl ethers in the solvent (B) is preferably 5 to 50% by weight, more preferably 5 to 30% by weight.
In addition, in view of recent adaptability to slit coating (slit coat) systems corresponding to large substrates and the like, it is also preferable to use a solvent having a boiling point of 150 ℃ or higher in combination. In this case, the content of the high boiling point solvent is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 5 to 30% by weight, based on the total amount of the solvent (B). If the amount of the high boiling point solvent is too small, for example, precipitation and solidification of a dye component or the like may occur at the tip of the slit nozzle, and further, foreign matter defects may occur; in addition, if the amount of the high boiling point solvent is too large, the drying rate of the composition becomes slow, and further, problems such as a defective production rhythm (tact) and pin hole marks of pre-baking (pre-cake) may occur in a reduced pressure drying process in a color filter manufacturing process described later.
The solvent having a boiling point of 150 ℃ or higher may be a glycol alkyl ether acetate or a glycol alkyl ether, and in this case, the solvent having a boiling point of 150 ℃ or higher may not be separately contained.
The content of the solvent (B) in the colored resin composition of the present invention is not particularly limited, and the upper limit thereof is usually 99% by weight. When the content of the solvent (B) in the composition exceeds 99% by weight, the concentration of each component other than the solvent (B) may become too small, and thus the composition is not suitable for forming a coating film. On the other hand, the lower limit of the content of the (B) solvent is usually 75% by weight, preferably 80% by weight, and more preferably 82% by weight in view of the viscosity suitable for coating and the like.
[ (C) Binder resin ]
The preferred resin for the (C) binder resin varies depending on the curing method.
When the colored resin composition of the present invention is a photopolymerizable resin composition, the binder resin (C) may be, for example, a polymer compound described in each of Japanese patent application laid-open Nos. 7-207211, 8-259876, 10-300922, 11-140144, 11-174224, 2000-56118, 2003-233179 and the like, and among them, the following resins (C-1) to (C-5) are preferable.
(C-1): a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer is a resin obtained by adding at least a part of the epoxy groups of the copolymer to an unsaturated monobasic acid, or an alkali-soluble resin (hereinafter, sometimes referred to as "resin (C-1)") obtained by adding at least a part of the hydroxyl groups formed by the addition reaction to a polybasic acid anhydride
(C-2): straight-chain alkali-soluble resin (C-2) having carboxyl group (hereinafter, may be referred to as "resin (C-2)")
(C-3): a resin obtained by adding an unsaturated compound having an epoxy group to the carboxyl group of the resin (C-2) (hereinafter, may be referred to as "resin (C-3)")
(C-4): (meth) acrylic resin (hereinafter, may be referred to as "resin (C-4)")
(C-5): epoxy acrylate resin having carboxyl group (hereinafter, sometimes referred to as "resin (C-5))
Among them, the resin (C-1) is particularly preferable, and the resin will be described below.
The resins (C-2) to (C-5) may be the same as those described in the same item in Japanese patent application laid-open No. 2009-025813, as long as they are soluble in an alkaline developer and have a solubility sufficient to complete the intended development treatment. The same applies to the preferred embodiment.
(C-1): a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, a resin obtained by adding at least a part of the epoxy groups of the copolymer to an unsaturated monobasic acid, or an alkali-soluble resin obtained by adding at least a part of the hydroxyl groups generated by the addition reaction to a polybasic acid anhydride
As one of particularly preferable resins of the resin (C-1), there can be mentioned: a resin obtained by adding 10 to 100 mol% of epoxy groups contained in a copolymer of 5 to 90 mol% of an epoxy group-containing (meth) acrylate and 10 to 95 mol% of another radical polymerizable monomer to an unsaturated monobasic acid, or an alkali-soluble resin obtained by adding 10 to 100 mol% of hydroxyl groups generated by the addition reaction to a polybasic acid anhydride.
Examples of the epoxy group-containing (meth) acrylate include: glycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, (3, 4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. Among them, glycidyl (meth) acrylate is preferable. The epoxy group-containing (meth) acrylate may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The other radically polymerizable monomers to be copolymerized with the epoxy group-containing (meth) acrylate are not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include: vinyl aromatics, dienes, (meth) acrylates, (meth) acrylamides, vinyl compounds, unsaturated dicarboxylic diesters, and monomaleimides, and mono (meth) acrylates having a structure represented by the following formula (7) are particularly preferable.
The content ratio of the repeating unit derived from the mono (meth) acrylate having a structure represented by the following formula (7) in the repeating unit derived from the "other radical polymerizable monomer" is preferably 5 to 90 mol%, more preferably 10 to 70 mol%, and particularly preferably 15 to 50 mol%.
[ chemical formula 68]
Figure BDA0001544982900000751
In the above formula (7), R89Represents a hydrogen atom or a methyl group, R90Represents a structure represented by the following formula (8).
[ chemical formula 69]
Figure BDA0001544982900000752
In the above formula (8), R91～R98Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In addition, R is96And R98Optionally joined to each other to form a ring.
R96And R98The ring formed by the linkage is preferably an aliphatic ring, and mayIn either case of a saturated ring or an unsaturated ring, the number of carbon atoms is preferably 5 to 6.
Among them, among the structures represented by formula (8), the structures represented by the following structural formulae (8a), (8b), or (8c) are particularly preferable.
[ chemical formula 70]
Figure BDA0001544982900000761
The mono (meth) acrylate having the structure represented by the above formula (8) may be used alone in 1 kind, or 2 or more kinds may be used in combination.
As the "other radical polymerizable monomer" other than the mono (meth) acrylate having the structure represented by the above formula (8), there can be mentioned, from the viewpoint of being able to improve the heat resistance and strength of the colored resin composition: styrene, N-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide.
The content of the repeating unit derived from at least 1 kind selected from the above monomer group is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.
In the copolymerization reaction of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer, a known solution polymerization method can be used.
In the present invention, the copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer is preferably a copolymer comprising 5 to 90 mol% of a repeating unit of the epoxy group-containing (meth) acrylate and 10 to 95 mol% of a repeating unit of the other radically polymerizable monomer, more preferably a copolymer comprising 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and particularly preferably a copolymer comprising 30 to 70 mol% of the former and 70 to 30 mol% of the latter.
When the amount is within the above range, the amount of addition of the polymerizable component and the alkali-soluble component described later is sufficient, and the heat resistance and strength are sufficient, so that the use is preferable.
The epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).
Here, as the unsaturated monobasic acid to which the epoxy group is added, a known compound can be used, and for example, an unsaturated carboxylic acid having an ethylenically unsaturated double bond can be cited.
Specific examples thereof include (meth) acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, monocarboxylic acids such as (meth) acrylic acid substituted at the α -position with a haloalkyl group, an alkoxy group, a halogen atom, a nitro group, a cyano group or the like, and among these, (meth) acrylic acid is preferable, and these unsaturated carboxylic acids may be used alone in 1 kind or in combination of 2 or more kinds.
The addition of the above components can impart polymerizability to the binder resin used in the present invention.
Usually, the unsaturated monobasic acid is added to 10 to 100 mol% of the epoxy group in the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. When the content is within the above range, the colored resin composition is preferably excellent in stability with time. Among them, as a method for adding an unsaturated monobasic acid to an epoxy group of the copolymer, a known method can be used.
Further, as the polybasic acid anhydride to be added to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer, a known polybasic acid anhydride can be used.
Examples thereof include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and hexachloronorbornenic anhydride; trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, biphenyl tetracarboxylic anhydride, and other three-or more-membered acid anhydrides. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferable. These polybasic acid anhydrides may be used alone in 1 kind, or 2 or more kinds may be used in combination.
The addition of the above components can impart alkali solubility to the binder resin used in the present invention.
Usually, 10 to 100 mol%, preferably 20 to 90 mol%, more preferably 30 to 80 mol% of hydroxyl groups formed by adding an unsaturated monobasic acid to the epoxy groups of the copolymer are added to the polybasic acid anhydride.
When the amount is within the above range, the residual film ratio and solubility at the time of development are sufficient, and therefore, the preferable range is obtained.
As a method for adding the hydroxyl group to the polybasic acid anhydride, a known method can be used.
In order to improve the photosensitivity, after the addition of the polybasic acid anhydride, a part of the carboxyl groups formed may be added to glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group. The structure of such a resin is described in, for example, Japanese patent application laid-open Nos. 8-297366 and 2001-89533.
The weight average molecular weight (Mw) of the binder resin (C-1) in terms of polystyrene measured by GPC (gel permeation chromatography) is preferably 3000 to 100000, and particularly preferably 5000 to 50000. If the molecular weight is less than 3000, deterioration of heat resistance and film strength may result; on the other hand, if it exceeds 100000, the solubility in the developer tends to be insufficient. Further, the ratio of the weight average molecular weight (Mw)/number average molecular weight (Mn) is preferably 2.0 to 5.0 as a rough criterion of the molecular weight distribution.
The acid value of the binder resin (C-1) is usually 10 to 200mg-KOH/g, preferably 15 to 150mg-KOH/g, and more preferably 25 to 100 mg-KOH/g. If the acid value is too low, the solubility in the developer may be lowered. On the contrary, if the acid value is too high, film cracking sometimes occurs.
The content of the binder resin (C) is usually 0.1 to 80% by weight, preferably 1 to 60% by weight, based on the total solid content.
Within the above range, the adhesion to the substrate is good, the permeability of the developing solution in the exposed portion is moderate, and the surface smoothness and sensitivity of the pixel are good, which is preferable.
[ (E) polymerizable monomer ]
When the polymerizable monomer (E) is contained in the colored resin composition of the present invention, the crosslinking density in the film is easily controlled, which is preferable.
As the polymerizable monomer (E), known materials can be used, but a compound having an ethylenically unsaturated double bond is preferable in view of low dark reactivity in the colored resin composition.
The olefinic compound is a compound having an olefinic double bond which is cured by addition polymerization under the action of a photopolymerization initiator described later when the colored resin composition of the present invention is irradiated with actinic light. The polymerizable monomer (E) in the present invention is a concept corresponding to a so-called polymer substance, and includes a dimer, a trimer, and an oligomer in addition to a monomer in a narrow sense.
Examples of the olefinic compound include: unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds with unsaturated carboxylic acids; esters of aliphatic polyols with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; esters obtained by esterification of unsaturated carboxylic acids with polycarboxylic acids and polyhydric hydroxyl compounds such as the above-mentioned aliphatic polyhydric compounds and aromatic polyhydric compounds; an olefinic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a hydroxyl compound containing a (meth) acryloyl group; and so on.
As the ester of an aliphatic polyhydric compound with an unsaturated carboxylic acid, there can be mentioned: (meth) acrylates such as ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and glycerol (meth) acrylate. Further, itaconate esters in which the (meth) acrylic acid moiety of these (meth) acrylate esters is replaced with an itaconic acid moiety, crotonate esters in which the (meth) acrylic acid moiety of these (meth) acrylate esters is replaced with a crotonic acid moiety, and maleate esters in which the (meth) acrylic acid moiety of these (meth) acrylate esters is replaced with a maleic acid moiety.
As the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, there can be mentioned: hydroquinone di (meth) acrylate, resorcinol di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like.
The ester obtained by esterification of an unsaturated carboxylic acid with a polycarboxylic acid and a polyhydroxyl compound is not necessarily a single compound, and may be a mixture. As representative examples, there may be mentioned: a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol; a condensate of (meth) acrylic acid, maleic acid, and diethylene glycol; a condensate of (meth) acrylic acid, terephthalic acid, and pentaerythritol; and condensates of (meth) acrylic acid, adipic acid, butanediol, and glycerin.
As the olefinic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxyl compound, there can be mentioned: aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; a reaction product of an aromatic diisocyanate such as tolylene diisocyanate or diphenylmethane diisocyanate and a (meth) acryloyl group-containing hydroxyl compound such as 2-hydroxyethyl (meth) acrylate or 3-hydroxy [1,1, 1-tri (meth) acryloyloxymethyl ] propane.
Further, as examples of the olefinic compound used in the present invention, there may be mentioned: (meth) acrylamides such as ethylenebis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate and the like.
Among the above, esters of aliphatic polyhydric compounds and unsaturated carboxylic acids are preferable, and (meth) acrylates of pentaerythritol or dipentaerythritol are more preferable, and dipentaerythritol hexa (meth) acrylate is particularly preferable.
In addition, the olefinic compound may also be a monomer having an acid value. Examples of the monomer having an acid value include esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, preferably polyfunctional monomers having an acid group obtained by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride, and particularly preferably monomers in which the aliphatic polyhydroxy compound in the ester is pentaerythritol and/or dipentaerythritol.
Although 1 kind of the above monomer may be used alone, a mixture of 2 or more kinds may be used because it is difficult to obtain a single compound from the viewpoint of production.
Further, as the (E) polymerizable monomer, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as needed.
The preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40mg-KOH/g, and particularly preferably 5 to 30 mg-KOH/g. If the acid value of the polyfunctional monomer is too low, a decrease in the developing dissolution property is caused; if the acid value of the polyfunctional monomer is too high, the production and handling may become difficult, and the photopolymerization performance may be lowered, resulting in poor curability such as surface smoothness of pixels. Therefore, in the case of using 2 or more kinds of polyfunctional monomers having different acid groups in combination, or using polyfunctional monomers having no acid group in combination, it is preferable to adjust the acid groups so that the acid groups of all the polyfunctional monomers fall within the above range.
In the present invention, a more preferred polyfunctional monomer having an acid group is a mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinate of dipentaerythritol pentaacrylate, which are commercially available from "TO 1382" manufactured by east asia synthetic company. The polyfunctional monomer may also be used in combination with other polyfunctional monomers.
In the colored resin composition of the present invention, the content of the polymerizable monomer (E) is usually 1% by weight or more, preferably 5% by weight or more, and more preferably 10% by weight or more, and usually 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less, in the total solid content.
The proportion of the polymerizable monomer (E) to the total color material including the dye (a) is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 20% by weight or more, and is usually 200% by weight or less, preferably 100% by weight or less, and more preferably 80% by weight or less.
Within the above range, the light effect is sufficient, adhesion failure and the like are not likely to occur during development, a cross section after development is not likely to be in an inverted conical shape, and peeling phenomenon, mold release failure and the like due to a decrease in solubility are not likely to occur, and therefore, such a range is preferable.
[ (F) photopolymerization initiating component and/or thermal polymerization initiating component ]
In order to cure the coating film, the colored resin composition of the present invention preferably contains (F) at least one of a photopolymerization initiating component and a thermal polymerization initiating component. The curing method may be a method in which these initiators are not used.
In particular, when the colored resin composition of the present invention contains a resin having an ethylenic double bond as the component (C) and an ethylenic compound as the component (E), it is preferable to contain a photopolymerization initiating component having a function of directly absorbing light or causing photosensitization to cause a decomposition reaction or a dehydrogenation reaction to generate a polymerization active radical and/or a thermal polymerization initiating component generating a polymerization active radical by heat. In the present invention, the component (F) as the photopolymerization initiating component is: a mixture of additives such as a polymerization accelerator (hereinafter, referred to as an (F2) component) and a sensitizing dye (hereinafter, referred to as an (F3) component) is used in combination with a photopolymerization initiator (hereinafter, referred to as an (F1) component).
(photopolymerization initiating component)
The colored resin composition of the present invention particularly preferably contains (F) a photopolymerization initiator. The photopolymerization initiator is usually used as a mixture with a photopolymerization initiator (F1) and, if necessary, additives such as a polymerization accelerator (F2) and a sensitizing dye (F3), and has a function of directly absorbing light or photosensitizing to initiate a decomposition reaction or a dehydrogenation reaction to generate a polymerization active radical.
Examples of the (F1) photopolymerization initiator constituting the photopolymerization initiation component include: titanocene derivatives described in JP-A-59-152396 and JP-A-61-151197; hexaarylbiimidazole derivatives as described in Japanese unexamined patent publication Nos. H10-300922, H11-174224, and H2000-56118; halomethylation described in Japanese patent laid-open No. 10-39503 and the like
Figure BDA0001544982900000811
Oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl- α -amino acids such as N-phenylglycine, radical activators such as N-aryl- α -amino acid salts and N-aryl- α -amino acid esters, α -aminoalkylphenone derivatives, oxime ester derivatives described in Japanese patent laid-open No. 2000-80068, and the like.
Specific examples thereof include photopolymerization initiators described in, for example, International publication No. 2009/107734.
Among these photopolymerization initiators, α -aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.
Further, examples of oxime ester derivatives include: 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ketene-1- (O-acetyloxime), and the like.
Further, there can be enumerated: benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4' -methylthiophenyl) -2-morpholinyl-1-propanone, thioxanthone derivatives such as 2-ethylthioxanthone and 2, 4-diethylthioxanthone, benzoate derivatives, acridine derivatives, phenazine derivatives and anthrone derivatives.
Among the above photopolymerization initiators, α -aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable, and oxime ester derivatives are particularly preferable.
Examples of the (F2) polymerization accelerator used as needed include: alkyl esters of N, N-dialkylaminobenzoic acid such as ethyl N, N-dimethylaminobenzoate; 2-mercaptobenzothiazole, 2-mercaptobenzothiazole
Figure BDA0001544982900000821
Mercapto compounds having a heterocyclic ring such as oxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds, and the like.
The photopolymerization initiator (F1) and the polymerization accelerator (F2) may be used alone or in combination of 1 or more.
In order to improve the sensitivity, a sensitizing dye (F3) may be used as needed. As the sensitizing dye, an appropriate sensitizing dye can be used depending on the wavelength of the image exposure light source, and examples thereof include: xanthene dyes described in Japanese patent application laid-open Nos. 4-221958 and 4-219756; coumarin-based dyes having a heterocyclic ring as described in, for example, Japanese patent application laid-open Nos. 3-239703 and 5-289335; 3-oxocoumarin dyes described in, for example, Japanese patent application laid-open Nos. 3-239703 and 5-289335; a methylene-pyrrole dye described in Japanese patent laid-open No. 6-19240 and the like; and pigments having a dialkylaminobenzene skeleton described in Japanese patent laid-open Nos. Sho 47-2528, Sho 54-155292, Sho 45-37377, Sho 48-84183, Sho 52-112681, Sho 58-15503, Sho 60-88005, Sho 59-56403, Hei 2-69, Sho 57-168088, Hei 5-107761, Hei 5-210240, and Hei 4-288818.
(F3) The sensitizing dye may be used alone in 1 kind or in combination of 2 or more kinds.
In the colored resin composition of the present invention, the content of the photopolymerization initiator (F) is usually 0.1% by weight or more, preferably 0.2% by weight or more, and more preferably 0.5% by weight or more, and usually 40% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight or less, based on the total solid content.
When the amount is within the above range, the sensitivity to exposure light is good, and the solubility of the unexposed portion in the developer is sufficient, and development failure is less likely to occur, and the like, and therefore, the amount is preferable.
(thermal polymerization initiating component)
Specific examples of the thermal polymerization initiating component (thermal polymerization initiator) that can be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Among these, azo compounds are preferably used. More specifically, for example, a thermal polymerization initiator described in international publication No. 2009/107734 and the like can be used.
The thermal polymerization initiator may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
[ optional Components ]
In addition to the above components, the colored resin composition of the present invention may further contain: a surfactant, an organic carboxylic acid and/or an organic carboxylic acid anhydride, a thermosetting compound, a plasticizer, a dye other than the dye (A) of the present invention, a thermal polymerization inhibitor, a storage stabilizer, a surface protecting agent, an adhesion improver, a development improver, and the like. In the case where the pigment is contained as the coloring matter, a dispersant and a dispersing aid may be contained. As these optional components, various compounds described in, for example, Japanese patent laid-open No. 2007-113000 can be used.
[ dispersing agent ]
When the colored resin composition of the present invention contains a pigment, it preferably further contains a dispersant.
The dispersant of the present invention is not limited in its kind as long as it can disperse and stabilize the pigment.
For example, a cationic, anionic, nonionic, amphoteric or the like dispersant can be used, but a polymer dispersant is preferable. Specific examples thereof include: block copolymers, polyurethanes, polyesters, alkyl ammonium salts or phosphate ester salts of high molecular copolymers, cationic comb-graft polymers, and the like. Among these dispersants, block copolymers, polyurethanes, cationic comb-graft polymers are preferred. Particularly preferred are block copolymers, and among them, preferred are block copolymers composed of an a block having solvent-affinity and a B block having a functional group containing a nitrogen atom.
Specifically, examples of the B block having a functional group containing a nitrogen atom include a unit structure having a quaternary ammonium salt group and/or an amino group in a side chain; on the other hand, the solvent-philic a block has a unit structure without a quaternary ammonium salt group and an amino group.
The B block constituting the acrylic block copolymer has a unit structure containing a quaternary ammonium salt group and/or an amino group, and is a site having a pigment adsorbing function.
In addition, as the B block, in the case of having a quaternary ammonium salt group, the quaternary ammonium salt group can be directly bonded to the main chain, or can be bonded to the main chain through a 2-valent linking group.
Examples of such block copolymers include those described in Japanese patent laid-open publication No. 2009-025813.
The colored resin composition of the present invention may contain a dispersant other than those described above. Examples of the other dispersant include dispersants described in Japanese patent application laid-open No. 2006-343648.
When the colored resin composition of the present invention contains a pigment, the content of the dispersant used is preferably 2 to 1000% by weight, particularly preferably 5 to 500% by weight, and particularly preferably 10 to 250% by weight, based on the total content of the pigment, based on the total solid content.
When the amount is within the above range, the pigment dispersion stability can be further improved while ensuring good pigment dispersibility without affecting the heat resistance of the dye, and therefore, the preferable range is obtained.
[ dispersing auxiliary ]
The colored resin composition of the present invention may further contain a dispersing aid. The dispersion aid herein may be a pigment derivative, and examples of the pigment derivative include various compounds described in Japanese patent application laid-open Nos. 2001-220520, 2001-271004, 2002-179976, 2007-113000, and 2007-186681.
The content of the dispersion aid in the colored resin composition of the present invention is usually 0.1% by weight or more, and usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less, based on the total solid content of the pigment. Controlling the amount of addition within the above range is preferable because the effect as a dispersing aid can be exerted and further excellent dispersibility and dispersion stability can be obtained.
[ dispersing resin ]
The colored resin composition of the present invention may contain a part or all of the resin selected from the above-mentioned (C) binder resin or other binder resins as the following dispersion resin.
Specifically, in the "method for producing a colored resin composition" described later, by containing the binder resin (C) in addition to the above-mentioned components such as the dispersant, the dispersion stability of the pigment can be improved by the synergistic effect of the binder resin (C) and the dispersant. This is preferable because the amount of the dispersant added may be reduced. Further, it is preferable to improve the developability and the adhesion between the pixel and the substrate, and to prevent undissolved matter from remaining in the non-pixel portion of the substrate.
Thus, the binder resin (C) used in the dispersion treatment step is also referred to as a dispersion resin. The amount of the dispersion resin used is preferably about 0 to 200 wt%, more preferably about 10 to 100 wt%, based on the total amount of the pigment in the colored resin composition.
[ method for producing colored resin composition ]
In the present invention, the colored resin composition can be prepared by an appropriate method, for example, by mixing the above-mentioned (a) dye, (C) binder resin, and (D) chain transfer agent comprising the compound (I) together with (B) solvent and other additives.
In addition, as a production method in the case where the dye (a) and the pigment are further contained, the following methods may be mentioned: in a solvent containing a pigment, in the presence of a dispersant and a dispersion aid added as needed, and in some cases together with a part of the binder resin (C), the colorant dispersion is prepared by mixing and dispersing while pulverizing using, for example, a paint shaker, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. To the colored dispersion liquid, additives such as (a) a dye, (C) a binder resin, (D) a chain transfer agent, and if necessary, (E) a polymerizable monomer, (F) at least one of a photopolymerization initiator and a thermal polymerization initiator are added and mixed to prepare a colored resin composition.
[ use of colored resin composition ]
The colored resin composition of the present invention is usually in a state in which all the constituent components are dissolved or dispersed in a solvent. The colored resin composition is supplied onto a substrate to form a color filter, a liquid crystal display device, an organic EL display device, and other components.
That is, the colored resin composition of the present invention is preferably a colored resin composition for a color filter.
Hereinafter, as an application example of the colored resin composition of the present invention, application thereof as a color filter, and a liquid crystal display device (panel) and an organic EL display device using the same will be described.
< color Filter >
The color filter of the present invention has pixels formed of the colored resin composition of the present invention.
The following description is directed to a method of forming a color filter of the present invention.
The pixels of the color filter may be formed using various methods. Here, a case where a pixel is formed by photolithography using a photopolymerizable colored resin composition will be described as an example, but the manufacturing method is not limited to this method.
First, a black matrix is formed on the surface of a substrate so as to define portions where pixels are to be formed, as necessary, and the colored resin composition of the present invention is applied to the substrate, and then prebaked to evaporate the solvent, thereby forming a coating film. Next, the coating film is exposed through a mask, developed with an alkali developer, and then, unexposed portions of the coating film are dissolved and removed, followed by post-baking, thereby forming pixel patterns of red, green, and blue, and a color filter can be manufactured.
The substrate used for forming the pixels is not particularly limited as long as it is transparent and has appropriate strength, and examples thereof include: polyester resins, polyolefin resins, polycarbonate resins, acrylic resins, thermoplastic resin sheets, epoxy resins, thermosetting resins, various glasses, and the like.
Further, these substrates may be subjected to the following appropriate pretreatment as necessary: surface treatments such as film formation treatment, corona discharge treatment, and ozone treatment with a silane coupling agent, a polyurethane resin, and the like.
When the colored resin composition is applied to a substrate, there are Spin Coating, Wire bar Coating, flow Coating, Slit and Spin Coating, die Coating, roll Coating, spray Coating and the like. Among them, slit spin coating and die coating are preferable.
The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, and particularly preferably 0.8 to 5.0 μm in terms of the film thickness after drying.
Within the above range, it is preferable because the gap adjustment in the pattern development and liquid crystal cell formation steps is easy and a desired color is easily displayed.
Examples of the radiation used for forming the pixels include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays, and radiation having a wavelength of 190 to 450nm is preferable.
The light source for obtaining radiation having a wavelength of 190 to 450nm, which can be used for image exposure, is not particularly limited, and examples thereof include: lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; and laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. When light of a specific wavelength is used for irradiation, an optical filter may be used.
The exposure amount of the radiation is preferably 10 to 10000J/m2。
In addition, as the alkali developing solution, for example: inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogenphosphate, potassium hydrogenphosphate, sodium dihydrogenphosphate, potassium dihydrogenphosphate, and ammonium hydroxide; and aqueous solutions of organic basic compounds such as monoethanolamine/diethanolamine/triethanolamine, monomethylamine/dimethylamine/trimethylamine, monoethylamine/diethylamine/triethylamine, monoisopropylamine/diisopropylamine, n-butylamine, monoisopropanol/diisopropylalcohol/triisopropanolamine, ethyleneimine, ethylenediimine (ethylenediimine), tetramethylammonium hydroxide (TMAH), and choline.
The alkali developing solution may be added with an appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or the like, a surfactant, or the like. After the alkali development, water washing is usually performed.
As the developing method, any of a dip developing method, a spray developing method, a brush developing method, an ultrasonic developing method, and the like can be used. The developing conditions are preferably 5 to 300 seconds at room temperature (23 ℃).
The conditions of the developing treatment are not particularly limited, and the developing temperature is usually 10 ℃ or higher, preferably 15 ℃ or higher, more preferably 20 ℃ or higher, and usually 50 ℃ or lower, preferably 45 ℃ or lower, more preferably 40 ℃ or lower.
The developing method may be any of immersion developing, spray developing, brush developing, ultrasonic developing, and the like.
When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO may be formed on an image as it is and used as a part of a member such as a color display or a liquid crystal display device. In some applications such as a partially in-plane alignment type driving method (IPS mode), a transparent electrode may not be formed. In addition, in the vertical alignment type driving system (MVA mode), a rib (rib) may be formed. In addition, instead of the bead dispersion type spacer, a pillar structure (photosensitive spacer) may be formed by photolithography.
< liquid Crystal display device >
The liquid crystal display device of the present invention is a liquid crystal display device using the color filter of the present invention. The type and structure of the liquid crystal display device of the present invention are not particularly limited, and the color filter of the present invention can be assembled using a conventional method.
For example, the liquid crystal display device of the present invention can be formed by a method described in "handbook of liquid crystal devices" (journal of the japanese industrial press (japanese industrial nova ), release 29.9.1989, and 142 rd committee of japan society for academic initiative).
< organic EL display device >
In the production of an organic EL display device including the color filter of the present invention, the following method can be employed: for example, as shown in fig. 1, a multicolor organic EL element is produced by forming pixels 20 on a transparent support substrate 10 using the colored resin composition of the present invention to obtain a blue color filter, and laminating an organic light emitting body 500 on the blue color filter with an organic protective layer 30 and an inorganic oxide film 40 interposed therebetween.
As a lamination method of the organic light-emitting body 500, there can be mentioned: a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the color filter upper surface; a method of bonding the organic light emitting body 500 formed on another substrate to the inorganic oxide film 40. The organic EL element 100 thus manufactured can be applied to an organic EL display device of a passive drive system, and can also be applied to an organic EL display device of an active drive system.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the description of the following examples within the scope not exceeding the gist of the present invention.
< colored resin composition for Forming blue Pixel >
[ Synthesis of dye ]
(Synthesis of Compound A)
[ chemical formula 71]
Figure BDA0001544982900000881
(reaction 1)
A mixture of compound 2(5.02g, 20mmol), compound 1(14ml, 80mmol), sodium tert-butoxide (7.53g, 80mmol), toluene (100ml), palladium (II) acetate (0.55g, 2.45mmol), tri-tert-butylphosphine (10% in hexane, 10g, 4.94mmol) was heated under reflux under nitrogen for 10 hours. After cooling to room temperature, water was added and filtration was carried out with celite, and the filtrate was extracted with toluene and washed with water. The toluene layer was concentrated under reduced pressure, purified by silica gel column chromatography (silica gel 500g, hexane/ethyl acetate 10/1-8/1-6/1), and the resulting powder was washed with cold methanol to obtain compound a (4.59, yield 53%).
Synthesis example 1 Synthesis of dye (1)
[ chemical formula 72]
Figure BDA0001544982900000882
(reaction 2)
To a mixture of Compound A (39g, 89.3mmol), Compound 3(18.5g, 89.3mmol) and toluene (120ml) was added phosphorus oxychloride (12.2ml, 134mmol), and the mixture was refluxed for 3.5 hours. After returning to room temperature, water was added, extraction was performed with chloroform, and the chloroform layer was washed 3 times with saturated brine. Purification by silica gel column chromatography (silica gel 300g, chloroform/methanol 15/1) and washing of the resulting solid with hexane gave compound B (54.8g, yield 93%).
(reaction 3)
A mixture of compound B (29g, 43.8mmol), lithium bis (trifluoromethanesulfonyl) imide (12.6g, 43.8mmol) and methanol (175ml) was stirred at 50 ℃ for 1.5 h. Concentration under reduced pressure and washing of the resulting solid with methanol/water-1/2 gave dye (1) (33.59g, 84.5% yield).
Synthesis example 2 Synthesis of dye (2)
[ chemical formula 73]
Figure BDA0001544982900000891
(reaction 4)
To a mixture of compound 4(35.4g, 109mmol), compound 3(22.6g, 109mmol) and toluene (200ml), phosphorus oxychloride (15ml, 164mmol) was added, and the mixture was refluxed for 4 hours. After returning to room temperature, water was added, extraction was performed with chloroform, and the chloroform layer was washed 3 times with saturated brine. Purification by silica gel column chromatography (silica gel 300g, chloroform/methanol 10/1-8/1) and washing of the obtained solid with hexane gave compound C (20g, yield 33%).
(reaction 5)
A mixture of compound C (18g, 32.7mmol), lithium bis (trifluoromethanesulfonyl) imide (9.4g, 32.7mmol) and methanol (60ml) was stirred at 50 ℃ for 1 hour. Concentration under reduced pressure and washing of the resulting solid with methanol/water (1/2) gave dye (2) (17.7g, yield 68%).
(Synthesis example 3: Synthesis of dye (3))
[ chemical formula 74]
Figure BDA0001544982900000901
A mixture of compound 5(6.0g, 25 mmol; synthesized by the method described in International publication No. 2008/003604), compound 6(6.4ml, 50 mmol; manufactured by Tokyo Kasei Co., Ltd.), potassium carbonate (6.9g, 50mmol) and N-methyl-2-pyrrolidone (25ml) was heated and stirred at 110 to 125 ℃ for 4 hours. After cooling to room temperature, water was added, extraction was performed with toluene, and the toluene layer was washed with dilute hydrochloric acid and saturated brine and dried over anhydrous sodium sulfate. Concentration under reduced pressure gave 9.2g of a light tea oil. This pale brown oil was dissolved in ethanol (40ml), and a solution of sodium hydroxide (2g, 52.3mmol) in water (25ml) was added, followed by stirring at 85 ℃ for 1 hour. After cooling, the mixture was extracted with toluene, and the toluene layer was washed with saturated brine and dried over anhydrous sodium sulfate. The extract was concentrated under reduced pressure and purified by silica gel column chromatography (hexane/ethyl acetate: 3/1), whereby compound 7(5.95g, yield 94%) was obtained as a white powder.
[ chemical formula 75]
Figure BDA0001544982900000902
A mixture of compound 8(1.47g, 4.34 mmol: synthesized by the method described in International publication No. 2009/107734), compound 7(1.1g, 4.34mmol), toluene (30ml) and phosphorus oxychloride (0.6ml) was refluxed for 4 hours, cooled to room temperature, added with water and extracted with chloroform. The chloroform layer was concentrated under reduced pressure, and the mixture was purified by silica gel column chromatography (eluent: chloroform/methanol 15/1 to 10/1), and the resulting solid was washed with hexane to obtain compound 9(1.32g, yield 50%).
[ chemical formula 76]
Figure BDA0001544982900000911
A mixture of compound 9(8.9g, 14.6mmol), compound 10(4.2g, 14.6 mmol: tokyo chemical co., ltd.) and methanol (50ml) was stirred at 50 ℃ for 1.5 hours, then concentrated under reduced pressure, and the resulting solid was washed with methanol/water (1/2), whereby dye (3) (11.5g, yield 92.3%) was obtained.
Synthesis example 4 Synthesis of dye (4)
[ chemical formula 77]
Figure BDA0001544982900000912
N-Ethyl-p-toluidine (138 g, manufactured by Tokyo chemical Co., Ltd.) was dissolved in N, N-dimethylformamide (520ml), and after cooling in an ice bath, potassium tert-butoxide (115g) was added in small portions. Then, a solution of 4, 4' -difluorobenzophenone (37 g, manufactured by Tokyo chemical Co., Ltd.) in DMF (180ml) was added dropwise thereto over 30 minutes under cooling in an ice bath, followed by stirring at 50 ℃ for 3 hours. Water and toluene were added, the organic layer was separated, and the organic layer was washed with water. The organic layer was dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by silica gel column chromatography (hexane/ethyl acetate 15/1-10/1) gave compound D (63.6g) as a pale yellow solid.
[ chemical formula 78]
Figure BDA0001544982900000913
To a mixture of compound D (24g), compound 3(11.1g) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and toluene (130ml), phosphorus oxychloride (7.3ml) (manufactured by Wako pure chemical industries, Ltd.) was added, and the mixture was refluxed for 5 hours. After cooling to room temperature, water was added, extraction was performed with chloroform, and the organic layer was washed 3 times with saturated brine. The extract was concentrated under reduced pressure and purified by silica gel column chromatography (chloroform/methanol 12/1) to obtain compound E (34.8 g).
[ chemical formula 79]
Figure BDA0001544982900000921
A mixture of compound E (6.66g), lithium bis (trifluoromethanesulfonyl) imide (2.87 g, manufactured by Tokyo chemical Co., Ltd.), and methanol (100ml) was stirred at 40 ℃ for 30 minutes, then concentrated under reduced pressure, and the resulting solid was washed with a mixture of methanol/water (1/2), whereby dye (4) (6.51g) was obtained.
Synthesis example 5 Synthesis of dye (5)
(Synthesis of intermediate C1)
[ chemical formula 80]
Figure BDA0001544982900000922
To a mixture of intermediate D (24g), 1-methyl-2-phenylindole (11.1g, manufactured by Tokyo Kasei Kogyo Co., Ltd.) and toluene (130ml), phosphorus oxychloride (7.3ml, manufactured by Wako pure chemical industries, Ltd.) was added, and the mixture was refluxed for 5 hours. After cooling to room temperature, water was added, extraction was performed with chloroform, and the organic layer was washed 3 times with saturated brine. After drying over anhydrous sodium sulfate, concentration under reduced pressure and purification by silica gel column chromatography (chloroform/methanol: 12/1) gave intermediate C1(34.8 g).
[ chemical formula 81]
Figure BDA0001544982900000923
A mixture of intermediate C1(6.0g) and 95% sulfuric acid (90g) was stirred at 70 ℃ for 6 hours and at 80 ℃ for 4 hours, then, ice water was poured in, and the precipitate was collected by filtration. After dissolving in acetone and diluting with water, the pH was adjusted to 8 with a 1N aqueous solution of sodium hydroxide, and the precipitate was filtered and dried to obtain dye 1(5.4 g). By passing1H NMR analysis revealed that dye (5) was a 64:36 mixture of dye (5) A and dye (5) B.
[ chemical formula 82]
Figure BDA0001544982900000931
1The results of H NMR and MS are shown below.
1H NMR(500MHz、CD3OD)δ1.25(t,H-4)、2.39(s,H-1)、3.88(m,H-5,H-11)、6.4-6.8(br,H-6)、7.00(d,H-15)、7.12(d,H-3),7.23-7.38(m,H-2,H-7,H-8,H-9,H-10)、7.60(d,H-12)、7.63(dd,H-16)、7.71(d,H-14)、7.87(dd,H-13)、8.11(d,H-17)
MS(LDI,posi)m/z 718(M+H,C46H44N3O3S)、740(M+Na,C46H43N3NaO3S)。
[ chemical formula 83]
Figure BDA0001544982900000932
Synthesis example 6 Synthesis of dye (6)
Acid red 289 (22.29 g, manufactured by Tokyo chemical industry Co., Ltd.) was added to chloroform (222.9g) and N, N-dimethylformamide (13.225g), and thionyl chloride (16.19g) was added dropwise while keeping the internal temperature at 20 ℃ or lower. After the dropwise addition, the temperature was raised, the reaction was carried out at 50 ℃ for 5 hours, then the reaction mixture was cooled to 20 ℃ or lower, and a mixture of triethylamine (32.8g, 0.324mol) and 2-ethylhexylamine (18.57g, 0.1436mol) was added dropwise thereto over 35 minutes while maintaining the temperature at 20 ℃ or lower. Then, it was stirred at room temperature for 5 hours. The solvent was concentrated, methanol (15ml) was added thereto, and after stirring sufficiently, the mixture was added dropwise to water (557g) with stirring to precipitate red crystals. The resin-like portion was dissolved in methanol again, concentrated, and crystallized by adding water again. The once-filtered crystals were subjected to suspension washing with water (300ml) and dried under reduced pressure to obtain dye (6) (21.823 g).
[ chemical formula 84]
Figure BDA0001544982900000941
[ Synthesis of resin ]
(reference Synthesis example 1: Synthesis of resin A)
Propylene glycol monomethyl ether acetate (145 parts by weight) was stirred while being replaced with nitrogen, and the temperature was raised to 120 ℃. To this solution, 82 parts by weight of styrene (20 parts by weight), glycidyl methacrylate (57 parts by weight) and a monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi chemical Co., Ltd.) were added dropwise, followed by stirring at 120 ℃ for 2 hours. Then, the inside of the reaction vessel was replaced with air, and 0.7 part by weight of tris (dimethylaminomethyl) phenol and 0.12 part by weight of hydroquinone were added to 27 parts by weight of acrylic acid, and the reaction was continued at 120 ℃ for 6 hours. Then, 52 parts by weight of tetrahydrophthalic anhydride (THPA) and triethylamine (0.7 part by weight) were added and reacted at 120 ℃ for 3.5 hours. The weight average molecular weight Mw of the resin a obtained above was about 15000 measured by GPC. The structure of the resin a is shown below (a polymer compound containing the following 4 kinds of repeating units).
[ chemical formula 85]
Figure BDA0001544982900000942
[ preparation of blue pigment Dispersion ]
A stainless steel container was filled with 11.36 parts by weight of c.i. pigment blue 15:6 as a blue pigment, 57.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 3.02 parts by weight of a dispersant "Disperbyk 2000" (manufactured by BYK Chemie) in terms of solid content, and 215.7 parts by weight of zirconia beads having a diameter of 0.5mm, and the mixture was dispersed in a paint shaker for 6 hours to prepare a blue pigment dispersion.
[ preparation of colored resin composition ]
The respective dyes obtained in [ synthesis of dyes ] and the resin a obtained in [ synthesis of resin ] were mixed with other components to have the compositions shown in tables 1 to 3, thereby preparing colored resin compositions. The numerical values in tables 1 to 3 represent the parts by weight of the solid content of the resist. The solid content in the resist was 22%, and the solvent composition was PGMEA (propylene glycol monomethyl ether acetate) and PGME (propylene glycol monomethyl ether) was 7: 3.
During mixing, the mixture was stirred for 1 hour or more until the respective components were sufficiently mixed, and finally filtered by a 5 μm cover plate type filter ( type フィルター) to remove foreign matters.
The numerical values in tables 1 to 3 represent the parts by weight of each component added.
Figure BDA0001544982900000961
Figure BDA0001544982900000971
Figure BDA0001544982900000981
< production of colored resin film and evaluation of solvent resistance >
Each of the colored resin compositions was applied by spin coating to a glass substrate cut into 5cm square, and the thickness of the dried film was set to 1.8 μm, and after drying under reduced pressure, prebaked (pre-cake) on a hot plate at 80 ℃ for 3 minutes. Then, at 60mJ/cm2After exposure of the entire surface, the substrate was baked in a dust-free oven at 230 ℃ for 30 minutes. Then, the spectral transmittance was measured by a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the chromaticity (light source C) in the XYZ color system was calculated.
Next, the substrate was immersed in PGMEA for 30 minutes, and then the spectral transmittance was measured in the same manner as described above to calculate the chromaticity (C light source) in the XYZ color system. The results of measurement of the color difference (Δ Ε ab) from the color after immersion, that is, the solvent resistance, are summarized in tables 4 to 6.
The results of measurements on the above-mentioned substrate by means of a spectrophotometer U-3310 (manufactured by Hitachi Co., Ltd.) are shown in tables 7 and 8.
[ Table 4]
TABLE 4 comparison of solvent resistance
Figure BDA0001544982900000991
[ Table 5]
TABLE 5 comparison of solvent resistance
Figure BDA0001544982900001001
[ Table 6]
TABLE 6 comparison of solvent resistance
Figure BDA0001544982900001002
[ Table 7]
TABLE 7 Brightness of colored resin composition comprising blue pigment and dye
Luminance Y
Example 13 10.46
Comparative example 2 10.40
[ Table 8]
TABLE 8 coloring including blue pigments and dyes
Brightness of resin composition
Luminance Y
Example 19 10.23
Example 20 10.55
Example 21 10.43
Example 22 10.02
Example 23 37.7
Comparative example 3 10.03
Comparative example 4 10.24
Comparative example 5 10.13
Comparative example 6 9.83
Comparative example 7 36.6
As is apparent from tables 4 to 6, the pixels formed using the colored resin composition of the present invention have extremely excellent solvent resistance.
As shown in tables 7 and 8, the pixels formed using the colored resin composition of the present invention had high luminance.
From this, it was found that a liquid crystal display device having pixels formed using the colored resin composition of the present invention has high image quality.
< colored resin composition for Forming Green Pixel >
[1] Synthesis of yellow dyes
< synthetic example 1: synthesis of Compound (1-i) >
117 parts by weight of 4-acetamidobenzenesulfonyl chloride, 1600 parts by weight of methylene chloride, 56 parts by weight of triethylamine and 3 parts by weight of 4-dimethylaminopyridine were added to a four-necked flask, and the mixture was cooled to 5 ℃. Subsequently, 71 parts by weight of 1, 5-dimethylhexylamine was added dropwise over 15 minutes, followed by stirring at room temperature for 6 hours. The organic layer was washed 2 times with 1000 parts by weight of 1mol/L hydrochloric acid, then with 1000 parts by weight of a saturated aqueous sodium hydrogencarbonate solution, and the resulting organic layer was dried over anhydrous sodium sulfate. After the drying agent was filtered off, the solvent was distilled off to obtain 154 parts by weight of a white solid of intermediate (i-a).
[ chemical formula 86]
Figure BDA0001544982900001021
98 parts by weight of intermediate (i-a) and 250 parts by weight of 5% by weight hydrochloric acid were charged in a four-necked flask, and after stirring at 90 ℃ for 5 hours, white solid (1-b) was obtained. This white solid was used for the subsequent reaction without purification.
[ chemical formula 87]
Figure BDA0001544982900001022
To the suspension containing (i-b) above, 1000 parts by weight of water and 24 parts by weight of concentrated hydrochloric acid were added, cooled to 5 ℃, and 8 parts by weight of sodium nitrite was added and stirred for 30 minutes. 26 parts by weight of 1- (2-ethylhexyl) -1, 2-dihydro-6-hydroxy-4-methyl-2-oxo-3-pyridinenitrile was added to a mixed solution of 80 parts by weight of methanol and 50 parts by weight of water, and while cooling to 5 ℃ and maintaining the pH at 8 with sodium hydroxide, a solution containing the diazo compound was added dropwise
Figure BDA0001544982900001023
A solution of a salt. By suction filtration of the reaction solution, an orange solid was obtained. This solid was purified by silica gel chromatography to obtain 66 parts by weight of a yellow solid of the compound (1-i).
[ chemical formula 88]
Figure BDA0001544982900001031
The maximum absorption wavelength (. lamda.max) of this compound in a 10ppm chloroform solution was 431nm, and the molar absorption coefficient was 87. The results of NMR are shown below.
1H NMR(CDCl3、400MHz)δ7.96(d,2H,J＝8.8Hz)、7.57(d,2H,J＝8.8Hz)、4.26(d,2H,J＝8.4Hz)、4.00-3.83(m,2H)、3.45-3.30(m,1H)、2.64(s,3H)、1.87-1.75(m,1H)、1.48-1.00(m,18H)、0.97-0.86(m,6H)、0.81(dd,6H,J＝6.4,2.4Hz)。
[2] Synthesis of resins
< reference Synthesis example 2: synthesis of resin B >
As a reaction vessel, a separable flask equipped with a cooling tube was prepared, 400 parts by weight of propylene glycol monomethyl ether acetate was added thereto, nitrogen gas was replaced, and the temperature of the reaction vessel was raised to 90 ℃ by heating in an oil bath with stirring.
On the other hand, 30 parts by weight of methyl 2, 2' - [ oxybis (methylene) ] bis 2-acrylate, 60 parts by weight of methacrylic acid, 110 parts by weight of cyclohexyl methacrylate, 5.2 parts by weight of t-butylperoxy-2-ethylhexanoate, and 40 parts by weight of propylene glycol monomethyl ether acetate were charged into a monomer tank, 5.2 parts by weight of n-dodecylmercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate were charged into a chain transfer agent tank, and after the temperature in the reaction tank was stabilized at 90 ℃, dropwise addition was started from the monomer tank and the chain transfer agent tank to initiate polymerization. The temperature was maintained at 90 ℃ and the dropwise addition was carried out over 135 minutes, and 60 minutes after the completion of the dropwise addition, the temperature was raised to 110 ℃.
After keeping at 110 ℃ for 3 hours, a gas inlet tube was provided in the separable flask, and bubbling of a mixed gas of 5/95(v/v) was started. Then, 39.6 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2, 2' -methylenebis (4-methyl-6-tert-butylphenol) and 0.8 part by weight of triethylamine were added to the reaction vessel, and the mixture was reacted at 110 ℃ for 9 hours while maintaining this state. The weight-average molecular weight Mw in terms of polystyrene of the resin B obtained above was 8000 and the acid value was 101mg-KOH/g as measured by GPC.
< reference synthesis example 3: synthesis of resin C >
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while being replaced with nitrogen, and the temperature was raised to 120 ℃. Thereto were added dropwise 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate, and 66 parts by weight of a monoacrylate FA-513M (manufactured by Hitachi chemical Co., Ltd.) having a tricyclodecane skeleton, and 8.47 parts by weight of 2.2' -azobis-2-methylbutyronitrile over 3 hours, followed by further stirring at 90 ℃ for 2 hours. Then, the reaction vessel was purged with air, and 43.2 parts by weight of acrylic acid were charged with 0.7 parts by weight of tris (dimethylaminomethyl) phenol and 0.12 parts by weight of hydroquinone, followed by further reaction at 100 ℃ for 12 hours. Then, 56.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 part by weight of triethylamine were added, and they were reacted at 100 ℃ for 3.5 hours. The polystyrene-reduced weight average molecular weight Mw of the resin C obtained above was about 8400 and the acid value was 80mg-KOH/g, as measured by GPC.
Then, propylene glycol monomethyl ether acetate was added to adjust the solid content concentration to 40%.
[3] Synthesis of photopolymerization initiator
The photopolymerization initiator (compound I-1) is shown below.
[ chemical formula 89]
Figure BDA0001544982900001041
Compound I-1 is synthesized based on the method described in Japanese patent application laid-open No. 2008-179611.
[4] Preparation of Green pigment Dispersion
12.7 parts by weight of C.I. pigment Green 58 (available from DIC) as a halogenated metal phthalocyanine pigment, 4.2 parts by weight of BYK Chemie "BYK-LPN 6919" (methacrylic AB block copolymer, amine number 121mg-KOH/g, acid number 1mg-KOH/g or less) as a dispersant in terms of solid content, and the resin B synthesized in reference Synthesis example 2 were mixed, and the solid content concentration was adjusted to 20% by using propylene glycol monomethyl ether acetate as a solvent. This mixed solution 100.5 parts by weight and zirconia beads having a diameter of 0.5mm 300 parts by weight were filled in a stainless steel container, and they were dispersed in a paint shaker for 6 hours, thereby preparing a green pigment dispersion.
[5] Preparation of colored resin composition
The dye synthesized in [1], the resin C synthesized in [2], the photopolymerization initiator synthesized in [3], the pigment dispersion prepared in [4], dipentaerythritol hexaacrylate as a polymerizable monomer, pentaerythritol tetrakis (3-mercaptopropionate) as a chain transfer agent (manufactured by Takara Shuzo Co., Ltd.) and a fluorine-based surfactant F-475 (manufactured by DIC Co., Ltd.) were diluted with 1% propylene glycol monomethyl ether acetate, and mixed at the ratio shown in Table 9, and propylene glycol monomethyl ether acetate was used as a solvent to prepare the colored resin compositions of examples and comparative examples so that the solid content concentration became 20%. The values in table 9 are the content (parts by weight) of the solvent-free component.
The following components were mixed and dissolved to prepare a colored photopolymerizable composition. The values in table 9 are the content (parts by weight) of the solvent-free component.
Figure BDA0001544982900001061
The numerical values in table 9 each represent parts by weight of each component added.
The compounds in table 9 are shown below.
PET-P: pentaerythritol Tetrakis (3-mercaptopropionate) (manufactured by Takara Shuzo Co., Ltd.)
DPHA: dipentaerythritol hexaacrylate
F475: fluorine type surfactant (manufactured by DIC Co., Ltd.)
[5] Measurement of dissolution time and residual film ratio
The colored resin compositions were applied to a glass substrate AN100 (manufactured by Asahi glass company) which was washed and cut into 5cm squares by a spin coating method, and dried under reduced pressure so that the dry film thickness was 2.0. mu.m. When the color resin composition in the unexposed area is subjected to spray development using a 0.04 wt% aqueous solution of potassium hydroxide at a developer temperature of 23 ℃ and a pressure of 0.25MPa, the time during which the color resin composition in the unexposed area is completely dissolved in the developer and the substrate is exposed is defined as the dissolution time of the color resin composition.
The glass substrate AN100 (manufactured by Asahi glass company) was washed, coated with the colored resin composition, and dried in the same manner as the measurement of the dissolution time. Then, at 50mJ/cm2The entire surface was exposed to light, and spray development was carried out using a 0.04 wt% aqueous solution of potassium hydroxide at a developer temperature of 23 ℃ and a pressure of 0.25 MPa. Here, the development time was set to the dissolution time +20 seconds. After the development, the substrate was washed with sufficient pure water and dried with clean air, and the film thickness of the colored resin composition remaining on the substrate was measured. The ratio of the film thickness after development, where the film thickness before development was 100%, was defined as the residual film ratio.
The results are summarized in Table 10.
[6] Measurement of the Width of the photocured portion (examples 24 to 27 and comparative examples 8 to 9) (line Width measurement)
With the above [5]]Measurement of dissolution time similarly, each colored resin composition was applied to a cleaned glass substrate AN100 (manufactured by asahi glass corporation) and dried. Then, using a mask having a line pattern of 40 μm in width and 30mm in length, at 50mJ/cm2The exposure was carried out at the exposure level of (1), and spray development was carried out using a 0.04 wt% aqueous solution of potassium hydroxide at a developer temperature of 23 ℃ and a pressure of 0.25 MPa.
The development was performed under two conditions of a dissolution time +10 seconds and a dissolution time +20 seconds.
After development, the resultant was washed with sufficient pure water, dried with clean air, and fired in an oven at 230 ℃ for 20 minutes. Then, the line width of the photocured portion was measured by a 50-fold optical microscope.
The results are summarized in Table 10.
Figure BDA0001544982900001081
As shown in table 10, even in the case where the colored resin composition containing the yellow dye did not contain the chain transfer agent, image formation was difficult (comparative examples 8 and 9).
On the other hand, the pixels formed using the colored resin composition of the present invention have high surface curability, and therefore, the film surface is not dissolved by alkali development at the exposed portion, and a high residual film ratio is exhibited, and good pixels can be formed in alkali development after exposure using a mask having a pattern (examples 24 to 27).
From these results, it was found that a pixel using a color filter including a pixel formed from the colored resin composition of the present invention was excellent in formation of a pixel, and that a liquid crystal display device and an organic EL display device including the color filter were high in quality.
While the present invention has been described in detail with reference to the specific embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The present application was completed based on japanese patent application published on 23/3/2011 (japanese patent application 2011-.

Claims (11)

1. A colored resin composition comprising (A) a dye, (B) a solvent, (C) a binder resin and (D) a chain transfer agent,
wherein the dye (A) comprises a triarylmethane dye, and the triarylmethane dye is at least one compound selected from the following formulas (II) to (V),
the chain transfer agent (D) is at least one selected from ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptopropionate),
the content of the dye (A) in the colored resin composition is 5 wt% or more based on the total solid content,
Figure FDA0002327723380000011
in the above formula (II), Zm1-Represents a disulfonylimide anion having a valence of m1,
m1 represents an integer of 1 to 4,
R1～R6each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted aromatic ring group, adjacent R1～R6May be bonded to each other to form a ring, which may have a substituent,
R7and R8Represents a hydrogen atom or an optional substituent, R7And R8Can be connected with each other to form a ring,
in addition, the benzene ring in the above formula (II) may further have an optional substituent,
when a molecule contains a plurality of structures represented by the following chemical formula, they may be the same structure or different structures,
Figure FDA0002327723380000021
in the above formula (III), Zm2-Represents an anion with the valence of m2,
m2 represents an integer of 1 to 4,
R11～R16each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted aromatic ring group, R11And R12、R13And R14And R15And R16Each of which may be bonded to each other to form a ring structure,
R17and R18Each independently represents a hydrogen atom or an optional substituent, R17And R18May be bonded to each other to form a ring,
in addition, the benzene ring and the indole ring in the above formula (III) may further have an optional substituent,
when a molecule contains a plurality of structures represented by the following chemical formula, they may be the same structure or different structures,
Figure FDA0002327723380000022
Figure FDA0002327723380000031
in the above-mentioned formula (IV),
R41～R46each independently represents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent,
adjacent R41～R46May be linked to each other to form a ring, which optionally has a substituent,
R47and R48Each independently represents a hydrogen atom or an optional substituent,
R47and R48May be linked to each other to form a ring, which may have a substituent,
further, the benzene ring and the indole ring in the formula (IV) may further have an optional substituent,
M+represents a hydrogen ion, an alkali metal cation, an alkaline earth metal cation, a tertiary ammonium cation or a quaternary ammonium cation,
n represents an integer of 0 to 4;
Figure FDA0002327723380000032
in the above formula (V), Rb1～Rb4Each independently represents a hydrogen atom, -Rb6Or an aromatic hydrocarbon group having 6 to 10 carbon atoms,
Rb5represents-SO3 -、-SO3H、-SO3M、-CO2H、-CO2Rb6、-SO3Rb6、-SO2NHRb8or-SO2NRb8Rb9，
m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of Rb5May be the same or different from each other,
Rb6represents a saturated hydrocarbon group having 1 to 10 carbon atoms,
Rb8and Rb9Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms or-Q1,
q1 represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms,
m represents a sodium atom or a potassium atom,
d represents a halogen atom, and a represents an integer of 0 or 1.
2. The colored resin composition according to claim 1, wherein the (D) chain transfer agent is pentaerythritol tetrakis (3-mercaptopropionate).
3. The colored resin composition according to claim 1, wherein the content of the chain transfer agent (D) is 2% by weight or more and 10% by weight or less in the total solid content.
4. The colored resin composition according to claim 1, wherein the compound represented by the formula (II) is a compound represented by the following formula (II-1),
Figure FDA0002327723380000041
in the formula, R1～R8With R in the above formula (II)1～R8The meaning is the same as that of the prior art,
R21and R22Each independently represents an alkyl group having 1 to 8 carbon atoms optionally substituted with a halogen atom, or a cycloalkyl group having 3 to 8 carbon atoms optionally substituted with a halogen atom,
in addition, R21And R22Can be bonded with each otherLooping.
5. The colored resin composition according to claim 1, further comprising (E) a polymerizable monomer.
6. The colored resin composition according to claim 5, wherein the polymerizable monomer (E) is a compound having an ethylenically unsaturated double bond.
7. The colored resin composition according to claim 1, further comprising (F) at least one of a photopolymerization initiating component and a thermal polymerization initiating component.
8. The colored resin composition according to claim 1, which is used for forming a blue pixel.
9. A color filter comprising a pixel formed using the colored resin composition according to any one of claims 1 to 8.
10. A liquid crystal display device having the color filter according to claim 9.
11. An organic EL display device having the color filter according to claim 9.
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Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014152256A (en) * 2013-02-08 2014-08-25 Mitsubishi Chemicals Corp Colored resin composition, color filter, liquid crystal display device and organic el display device
JP6457719B2 (en) * 2013-03-06 2019-01-23 株式会社Adeka Photocurable composition
JP2014189663A (en) * 2013-03-27 2014-10-06 Mitsubishi Chemicals Corp Colored resin composition, color filter, liquid crystal display device, and organic el display device
JP6135282B2 (en) * 2013-04-26 2017-05-31 大日本印刷株式会社 Color material, color material dispersion, colored resin composition for color filter, color filter, liquid crystal display device, and organic light emitting display device
TWI604272B (en) * 2013-05-24 2017-11-01 奇美實業股份有限公司 Blue photosensitive resin composition for color filter and uses thereof
TWI490644B (en) * 2013-08-09 2015-07-01 Chi Mei Corp Blue photosensitive resin composition for color filter and uses thereof
JP6496116B2 (en) * 2013-10-09 2019-04-03 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． Colored curable resin composition
JP2015113421A (en) * 2013-12-12 2015-06-22 三菱化学株式会社 Colored resin composition, color filter, liquid crystal display device, and organic electroluminescence (el) display device
JP6371601B2 (en) * 2014-06-20 2018-08-08 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． Compound and colored curable resin composition
JP6211713B2 (en) * 2014-09-08 2017-10-11 富士フイルム株式会社 Image forming material and image forming method
KR102092438B1 (en) * 2016-07-26 2020-03-23 주식회사 엘지화학 Photosensitive resin composition and color filter comprising same
KR102131481B1 (en) * 2016-07-26 2020-07-07 주식회사 엘지화학 Photosensitive resin composition and color filter comprising same
KR102092439B1 (en) * 2016-07-26 2020-03-23 주식회사 엘지화학 Photosensitive resin composition and color filter comprising same
CN107698536B (en) * 2016-08-08 2023-05-09 东友精细化工有限公司 Compound, coloring composition, fiber material, color filter and display device
JP7075724B2 (en) * 2016-08-08 2022-05-26 東友ファインケム株式会社 Compounds, coloring compositions, textile materials, color filters, and display devices
JP6971021B2 (en) * 2016-11-16 2021-11-24 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. Color curable resin composition, color filter, and display device
JP6931575B2 (en) * 2016-11-16 2021-09-08 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． Coloring composition, coloring curable resin composition, color filter and liquid crystal display device
JP6917950B2 (en) * 2017-08-23 2021-08-11 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． Color curable resin composition, color filter, and display device
TW202024137A (en) * 2018-12-20 2020-07-01 住華科技股份有限公司 Coloring resin composition, and color filter, liquid crsytal display device and organic electroluminescent display device using the same
JP2024129790A (en) 2023-03-13 2024-09-27 保土谷化学工業株式会社 Triarylmethane dye, coloring composition containing the dye, colorant for color filter, and color filter

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006139136A (en) * 2004-11-12 2006-06-01 Fuji Photo Film Co Ltd Composition for pattern formation, pattern forming material, and pattern forming apparatus and pattern forming method
CN101546122A (en) * 2008-03-26 2009-09-30 株式会社艾迪科 Color resist composition and a color filter using the same
CN101872122A (en) * 2009-04-24 2010-10-27 凸版印刷株式会社 Blue colored composition, color filter, liquid crystal indicator and OLED display

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3147423B2 (en) * 1991-09-05 2001-03-19 インターナショナル・ビジネス・マシーンズ・コーポレ−ション Color filter and manufacturing method thereof
JP2000249822A (en) * 1999-02-26 2000-09-14 Showa Denko Kk Photopolymerization initiator for color filter, photosensitive coloring composition and color filter
CN100523008C (en) * 2002-02-28 2009-08-05 昭和电工株式会社 Thiol compound, photopolymerization initiator composition and photosensitive composition
JP2006071890A (en) * 2004-09-01 2006-03-16 Fuji Photo Film Co Ltd Dye-containing negative curable composition, and color filter, and method for producing color filter
JP2006078602A (en) * 2004-09-07 2006-03-23 Fuji Photo Film Co Ltd Dye-containing negative-type curable composition, color filter and method for producing the same
JP4832973B2 (en) * 2006-07-26 2011-12-07 富士フイルム株式会社 Curable composition for color filter, color filter, and method for producing the same
JP4837603B2 (en) * 2007-03-14 2011-12-14 富士フイルム株式会社 Negative curable composition, color filter and method for producing the same
KR20090057814A (en) * 2007-12-03 2009-06-08 제일모직주식회사 Photosensitive resin composition for color filters and color filter manufactured using the same
JP5544725B2 (en) * 2008-02-27 2014-07-09 三菱化学株式会社 Colored resin composition for color filter, color filter, organic EL display and liquid crystal display device
TWI455984B (en) * 2008-05-30 2014-10-11 Sumitomo Chemical Co Colored hardening composite
CN101625525B (en) * 2008-07-11 2013-06-12 住友化学株式会社 Light-sensitive resin composition
JP2010224204A (en) * 2009-03-24 2010-10-07 Sumitomo Chemical Co Ltd Colored photosensitive resin composition
JP2010235739A (en) * 2009-03-31 2010-10-21 Toyo Ink Mfg Co Ltd Photosensitive black composition
JP5678411B2 (en) * 2009-04-07 2015-03-04 凸版印刷株式会社 Red coloring composition and color filter
JP5672677B2 (en) * 2009-08-21 2015-02-18 大日本印刷株式会社 Photosensitive resin composition for color filter, and color filter using the photosensitive resin composition
JP5705459B2 (en) * 2009-09-04 2015-04-22 富士フイルム株式会社 Photocurable composition for color filter, color filter formed with the photocurable composition, and image display device including the same
JP5493877B2 (en) * 2010-01-06 2014-05-14 凸版印刷株式会社 COLORING COMPOSITION CONTAINING DYE, COLOR FILTER AND METHOD FOR PRODUCING THE SAME, LIQUID CRYSTAL DISPLAY DEVICE AND ORGANIC EL DISPLAY DEVICE
JP5942368B2 (en) * 2010-09-13 2016-06-29 三菱化学株式会社 Colored resin composition, color filter, liquid crystal display device and organic EL display device
TWI516867B (en) * 2010-12-22 2016-01-11 富士軟片股份有限公司 Coloring photosensitive composition, color filter, method for fabricating color filter, and liquid crystal display apparatus
JP5696091B2 (en) * 2011-04-25 2015-04-08 富士フイルム株式会社 Photosensitive resin composition, color filter, protective film, photospacer, substrate for liquid crystal display device, liquid crystal display device and solid-state imaging device
JP5539429B2 (en) * 2012-03-19 2014-07-02 富士フイルム株式会社 Colored photosensitive composition, color filter, method for producing color filter, and liquid crystal display device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006139136A (en) * 2004-11-12 2006-06-01 Fuji Photo Film Co Ltd Composition for pattern formation, pattern forming material, and pattern forming apparatus and pattern forming method
CN101546122A (en) * 2008-03-26 2009-09-30 株式会社艾迪科 Color resist composition and a color filter using the same
CN101872122A (en) * 2009-04-24 2010-10-27 凸版印刷株式会社 Blue colored composition, color filter, liquid crystal indicator and OLED display

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