JP6686657B2 - Coloring composition, colored cured film, color filter, display device and solid-state imaging device - Google Patents

Description

  The present invention relates to a colored composition, a colored cured film, a color filter, a display device and a solid-state image pickup device, and more specifically, a transmissive or reflective color liquid crystal display device, a solid-state image pickup device, an organic EL display device, an electronic paper. The present invention relates to a colored composition used for forming a colored cured film used for the above, a colored cured film formed using the colored composition, a color filter including the colored cured film, a display element, and a solid-state imaging device.

  In producing a color filter using the colored radiation-sensitive composition, on a substrate, after coating the pigment-dispersed colored radiation-sensitive composition and drying, the dried coating film is irradiated with radiation in a desired pattern shape. A method of arranging pixels of three primary colors of red, green, and blue on a substrate by irradiating (hereinafter referred to as "exposure") and developing (so-called photolithography method, for example, see Patent Documents 1 and 2). Are known. Also known is a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (see, for example, Patent Document 3). Furthermore, a method of obtaining pixels of each color by an inkjet method using a pigment-dispersed colored resin composition (see, for example, Patent Document 4) is also known.

  In recent years, there has been a strong demand for higher contrast of liquid crystal display devices and higher definition of solid-state image pickup devices, and in order to realize these, application of dyes as colorants is being studied. However, when a dye is used as the coloring agent, the heat resistance of the coloring pattern is often insufficient as compared with the case where a pigment is used. Under such a background, as a colored composition capable of forming a colored pattern having excellent heat resistance and the like, for example, in Patent Document 5, a dye multimer having a polymerizable group as a colorant, a pigment, and a polymerizable compound are used. , A coloring composition containing a photopolymerization initiator has been proposed.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP, 2013-28764, A

However, the present inventors have found that the colored pattern formed using the colored composition described in Patent Document 5 has low developability and insufficient heat resistance and solvent resistance.
Therefore, an object of the present invention is to provide a colored composition capable of forming a colored cured film capable of achieving a well-balanced high level of heat resistance, solvent resistance and developability. A further object of the present invention is to provide a colored cured film formed by using the colored composition, and a color filter, a display device, and a solid-state imaging device having the colored cured film.

  As a result of intensive studies, the present inventors have found that a copolymer having a monomer having a specific structure as a binder resin in a specific copolymerization ratio together with at least one selected from dyes and dye multimers and a polymerizable compound. It was found that the above problem can be solved by containing

That is, the present invention is
(A) a colorant containing at least one selected from a dye and a dye multimer having a dye monomer having a dye residue and an ethylenically unsaturated group as a structural unit,
Including (B) a binder resin and (C) a polymerizable compound,
As the binder resin (B), a copolymer having a copolymerization ratio of the ethylenically unsaturated monomer represented by the following formula (1) of 11 mol% or more (excluding the dye multimer) is contained. A coloring composition.

[In Formula (1),
R ¹ represents a hydrogen atom or a methyl group,
R ² represents an alkanediyl group having 2 to 4 carbon atoms,
R ³ represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted polycyclic aromatic hydrocarbon group, or a substituted or unsubstituted nitrogen-containing alicyclic heterocyclic group,
n shows the integer of 0-100. However, when n is 2 or more, a plurality of R ^{2 s} may be the same or different. ]

  The present invention also provides a colored cured film formed by using the above colored composition, and a display device including the colored cured film. Here, the “colored cured film” means each color pixel, a protective film, a black matrix, a spacer, an insulating film, or the like used in a display element or a solid-state imaging element.

  According to the present invention, a colored cured film capable of achieving a well-balanced high level of heat resistance, solvent resistance, and developability, even though at least one selected from dyes and dye multimers is used as a colorant. A possible coloring composition can be provided. Therefore, the coloring composition of the present invention can be used for producing various color filters including color liquid crystal display devices, color filters for color separation of solid-state imaging devices, organic EL display device color filters, and electronic paper color filters. It can be used very suitably.

Hereinafter, the present invention will be described in detail.
Coloring Composition Hereinafter, the constituent components of the coloring composition of the present invention will be described in detail.

-(A) Colorant-
The coloring composition of the present invention contains (A) a dye as a colorant and at least one selected from a dye multimer having a dye monomer having a dye residue and an ethylenically unsaturated group as a structural unit.
First, the dye will be described.
The dye is not particularly limited, and the color and material can be appropriately selected according to the application such as a color filter, and one kind or a combination of two or more kinds can be used. As the dye used in the present invention, for example, a known dye can be used in addition to the compounds classified into Dye in the color index (CI; issued by The Society of Dyers and Colorists). .

  As such dyes, from the viewpoint of the structure of the chromophore, for example, xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, quinophthalone dyes, coumarin dyes. , Pyrazolone dyes, quinoline dyes, nitro dyes, quinonimine dyes, phthalocyanine dyes and the like.

Examples of the xanthene-based dye include compounds described in paragraph [0010] of JP-A-2013-053292, and compounds represented by formulas (A1) to (A6) described in Examples of JP-A-2013-100463. Compounds described in JP 2012-181505 A, paragraphs [0038] to [0043] and paragraphs [0048] to [0050], and JP 2013-007032 A, paragraphs [0036] to [0038]. Other compounds can be used. Examples of triarylmethane dyes include JP 2001-011336 A, JP 2003-246935 A, JP 2008-304766 A, International Publication No. 2010/123071, a pamphlet, and JP 2010-256598 A. JP2011-007847A, JP2011-070172A, JP2011-116803A, JP2011-117995A, JP2011-133844A, JP2011-227408A, and the international publication. No. 2011/152379 pamphlet, International publication No. 2011/162217 pamphlet, JP 2012-017425 A, JP 2012-037740 A, WO 2012/036085 pamphlet, JP 2012-073291. Publication, International Publication No. 2012/053201, Pamphlet, JP2012-083652A, JP2012-088615A, JP2012-098522A, JP2013-057053A, US Patent Application Publication 2013 / The compounds described in the specification of 0141810, the pamphlet of International Publication No. 2013/147099, etc. can be used.
Examples of cyanine dyes include components (A-2) to (A-6) described in Examples of JP-A-2009-235392, paragraphs [0096] to [0108] of JP-A-2012-212089. Compounds described in paragraphs [0054] to [0063] of JP 2012-214718 A, compounds described in paragraphs [0050] to [0054] of JP 2012-214719 A, etc. Can be used.

Examples of the anthraquinone dyes include compounds described in paragraph [0049] of JP2013-053292A, paragraphs [0071] of JP2000-129150A, and JP2008-0155530A. Compounds described in JP-A-2013-210621 and the like can be used.
Examples of azo dyes include JP 2003-510398 A, JP 2005-226022 A, JP 2007-212639 A, JP 2010-152160 A, JP 2010-170073 A, and JP 2011. -148993, JP2011-148994A, JP2011-148995A, JP2012-041461A, JP2012062461A, WO2012 / 039361A, JP2012-2012A. Pyridone azo dyes described in JP-A-194200; for example, JP-A-04-249549, JP-A-2005-120132, JP-A-2005-298636, JP-A-2007-197538, and JP-A-2010-275531. Japanese Patent Laid-Open No. 2012-2012 Diazo dyes described in JP-A-41429 and the like; for example, monoazo dyes described in JP-A-2004-325864 and JP-A-2010-275533; JP-A-2005-274788 and JP-A-2005-290351. Publications, JP-A-2006-039301, JP-A 2007-041076, JP-A 2007-041050, JP-A 2009-067748, JP-A 2010-170116, JP-A 2010-170117, etc. The pyrazole azo dyes described in JP-A 2007-293127, paragraphs [0058] to [0061], JP 2011-219655 A, paragraphs [0014], JP 2013-145258 A, etc. Besides azomethine dyes, JP 2010-150416 A JP, 2010-152159 A, JP 2010-170074 A, JP 2011-016974 A, JP 2011-074270 A, JP 2011-145540 A, US Patent Application Publication No. 2013/0164641. The compounds described in the specification can be used.

As the dipyrromethene dye, for example, in addition to the compounds described in JP 2008-292970 A, JP 5085256 A, etc., a dipyrromethene compound containing a polymerizable group described in JP 2011-180306 A, etc. may be used. You can
Examples of the quinophthalone dye include compounds represented by the formula (2) described in JP-A-5-039269, JP-A-6-220339, JP-A-8-171201, and JP-A-2006-126649. A compound represented by the formula (1) described in JP 2010-250291 A and a compound represented by the formula (1) described in JP 2013-209614 A can be used.
Examples of the coumarin dye include the compound described in Example 4 of JP-A-4-179955, the compound represented by the formula (1) described in JP-A-2013-151668, and JP-A-2013-231165. The compound represented by the formula (1) described in JP-A-2014-044419 and the compound represented by the formula (1) described in JP-A-2014-044419 can be used.
As the pyrazolone dye, for example, a compound represented by the formula (1) described in JP-A-2006-016564 or a compound represented by the formula (1) described in JP-A-2006-063171 may be used. You can
Examples of the phthalocyanine dye include compounds described in JP-A-2004-233504 and JP-A-2006-047497, and also described in paragraphs [0147] to [0155] of JP-A-2007-094181. A compound or the like can be used.

  As the dye, any of an acid dye, a basic dye and a nonionic dye can be preferably used. Here, in the present specification, the “acidic dye” means an ionic dye having an anion moiety as a chromophore, and an ionic dye forming a salt with the anion moiety is also an acid dye. Further, in the present specification, the “basic dye” means an ionic dye having a cation moiety as a chromophore, and an ionic dye forming a salt with the cation moiety is also a basic dye. "Nonionic dye" means a dye other than an acid dye and a basic dye.

  Examples of the acid dye include azo acid dyes, triarylmethane acid dyes, anthraquinone acid dyes, xanthene acid dyes, quinoline acid dyes, nitro acid dyes, cyanine acid dyes, and the like. The acid dyes can be used alone or in combination of two or more, and when two or more kinds are used in combination, they can be optionally combined.

Specific examples of the azo acid dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Mordant Red 7, C.I. I. Moldant Yellow 5, C.I. I. Moldant Black 7, C.I. I. Direct Green 28 and the like can be mentioned.
Specific examples of the triarylmethane-based acidic dye include, for example, C.I. I. Acid Blue 9 and the like can be mentioned.
Specific examples of the anthraquinone-based acid dye include C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49 and the like can be mentioned.
Specific examples of the xanthene-based acid dye include C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, C.I. I. In addition to Acid Red 388, the dyes disclosed in Synthesis Examples 1 to 3 of JP2010-32999A and JP2011-138094A can be exemplified.
Specific examples of the quinoline-based acid dye include, for example, C.I. I. Acid Yellow 3 and the like can be mentioned.
Specific examples of the nitro acid dye include C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3 and the like can be mentioned.
Specific examples of the cyanine-based acid dye include, for example, C.I. I. Reactive Yellow 1 and the like can be mentioned.

  Examples of the basic dyes include azo-based basic dyes, triarylmethane-based basic dyes, xanthene-based basic dyes, quinoneimine-based basic dyes, and cyanine-based basic dyes. The basic dyes can be used alone or in combination of two or more, and when two or more are used in combination, they can be optionally combined.

Specific examples of the azo basic dye include C.I. I. Basic Blue 41, C.I. I. Other than Basic Red 18, dyes described in JP2011-145540A can be used.
Specific examples of the triarylmethane-based basic dye include, for example, C.I. I. Basic Blue 7, C.I. I. In addition to Basic Green 1, pamphlets of International Publication No. 2010/123071, JP 2011-116803 A, JP 2011-117995 A, JP 2011-133844 A and the like can be mentioned.
Specific examples of the xanthene-based basic dye include C.I. I. Basic violet 11 etc. can be mentioned.
Specific examples of the quinone imine basic dye include C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like can be mentioned.
Specific examples of the cyanine-based basic dye include C.I. I. Basic Red 12, C.I. I. Basic Red 13, C.I. I. Basic Red 14, C.I. I. Basic Violet 7, C.I. I. Basic Violet 16, C.I. I. Basic Yellow 1, C.I. I. Basic Yellow 11, C.I. I. Basic Yellow 13, C.I. I. Basic Yellow 21, C.I. I. Basic Yellow 28, C.I. I. Basic Yellow 51 and the like can be mentioned.
In addition, various basic dyes described in JP-A-2007-503477 can be mentioned.

  Examples of nonionic dyes include azo nonionic dyes, anthraquinone nonionic dyes, phthalocyanine nonionic dyes, nitro nonionic dyes, and methine nonionic dyes. The nonionic dyes can be used alone or in combination of two or more, and when two or more kinds are used in combination, they can be optionally combined.

Specific examples of the azo nonionic dye include C.I. I. Disperse Orange 5, C.I. I. Disperse Red 58, C.I. I. In addition to Disperse Blue 165, dyes described in JP2010-170073A, JP2010-170074A, JP2010-275531A, and JP2010-275533A can be exemplified. Specific examples of the anthraquinone-based nonionic dye include C.I. I. Bat Blue 4, C.I. I. Disperse Red 60, C.I. I. Disperse Blue 56, C.I. I. Examples include Disperse Blue 60 and the like.
Specific examples of the phthalocyanine-based nonionic dye include, for example, C.I. I. Pad blue 5, etc. can be mentioned.
Specific examples of the quinoline-based nonionic dye include, for example, C.I. I. Solvent Yellow 33, C.I. I. Examples include Disperse Yellow 64 and the like.
Specific examples of the nitro-based nonionic dye include C.I. I. Examples include Disperse Yellow 42 and the like.
Specific examples of the methine nonionic dye include C.I. I. Solvent Yellow 179, Disperse Yellow 201 and the like can be mentioned.
In addition, various nonionic dyes described in claim 3 or claim 4 of JP 2010-168531 A can be mentioned.

  In the present invention, the dye is preferably an acid dye or a basic dye, and from the structural aspect of the chromophore, triarylmethane dyes, xanthene dyes, azo dyes, methine dyes, dipyrromethene dyes, cyanine dyes. Dyes are preferable, and dyes selected from triarylmethane dyes, xanthene dyes, dipyrromethene dyes and cyanine dyes are more preferable, and dyes selected from triarylmethane dyes, dipyrromethene dyes and cyanine dyes are more preferable. Triarylmethane dyes are more preferable.

Next, the dye multimer will be described.
The dye multimer has a dye monomer having a dye residue and an ethylenically unsaturated group as a structural unit. The dye multimers may be used alone or in combination of two or more.
As the dye residue, from the structural side of the chromophore, for example, xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, quinophthalone dyes, coumarin dyes, Examples thereof include residues of dyes selected from pyrazolone dyes, quinoline dyes, nitro dyes, quinonimine dyes, and phthalocyanine dyes. As used herein, the term "dye residue" refers to a residue obtained by removing one hydrogen atom from a dye compound. Among them, the dye residue is preferably a residue of a dye selected from triarylmethane dyes, xanthene dyes, azo dyes, dipyrromethene dyes, methine dyes, and cyanine dyes, and triarylmethane dyes. A residue of a dye selected from a xanthene dye, a dipyrromethene dye and a cyanine dye is more preferable, and a residue of a triarylmethane dye is further preferable. The dye residue may be derived from any of acid dyes, basic dyes and nonionic dyes, but acid dyes and basic dyes are preferred.
Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, and a (meth) acryloyl group.
Examples of such dye monomers include monomers represented by the following formula (2).

[In the formula (2),
R ¹¹ represents a hydrogen atom or a methyl group,
X ¹ is a single bond, a substituted or unsubstituted divalent hydrocarbon group, or a combination of the divalent hydrocarbon group and one or more linking groups containing atoms other than carbon atoms and hydrogen atoms 2 Indicates a valence group,
D ¹ represents a dye residue. ]

A hydrogen atom or a methyl group can be appropriately selected as R ¹¹ .
Examples of the divalent hydrocarbon group for X ¹ include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. In addition, in the present specification, the “alicyclic hydrocarbon group” is a concept excluding an aliphatic hydrocarbon group having no cyclic structure. The divalent aliphatic hydrocarbon group may be linear or branched, and the divalent aliphatic hydrocarbon group and the divalent alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. It may be a base. Further, in the present specification, the “alicyclic hydrocarbon group” and “aromatic hydrocarbon group” include not only a group consisting of only a ring structure but also a divalent aliphatic hydrocarbon group substituted on the ring structure. The above-mentioned group is also included, and it is sufficient that the structure contains at least an alicyclic hydrocarbon or an aromatic hydrocarbon.

Examples of the divalent aliphatic hydrocarbon group include an alkanediyl group and an alkenediyl group, and the carbon number thereof is preferably 1 to 20, more preferably 2 to 12, and further preferably 2 to 6. Specific examples include, for example, methylene group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-1, 3-diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4-diyl group, Pentane-1,5-diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, 2-methylpropane-1,2-diyl group, 2,2-dimethylpropane-1,3- Diyl group, ethene-1,1-diyl group, ethene-1,2-diyl group, propene-1,2-diyl group, propene-1,3-diyl group, propene-2,3-diyl group, 1- Butene-1,2-diyl group, 1-butene-1,3-diyl group 1-butene-1,4-diyl group, 2-pentene-1,5-diyl group, and a 3-hexene-1,6-diyl group.
Examples of the divalent alicyclic hydrocarbon group include a cycloalkylene group and a cycloalkenylene group, and the carbon number thereof is preferably 3 to 20, and more preferably 3 to 12. Specific examples include, for example, a monocyclic hydrocarbon ring group such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclobutenylene group, a cyclopentenylene group, and a cyclohexenylene group, 1,4 Examples thereof include a norbornylene group such as a -norbornylene group and a 2,5-norbornylene group, and a bridged ring hydrocarbon group such as a 1,5-adamantylene group and a 2,6-adamantylene group.
Examples of the divalent aromatic hydrocarbon group include an arylene group, and a monocyclic to tricyclic arylene group having 6 to 14 carbon atoms is preferable. Specific examples thereof include a phenylene group, a biphenylene group, a naphthylene group, a phenanthrene group, and an anthrylene group.

In the divalent group formed by combining a divalent hydrocarbon group and one or more linking groups containing atoms other than carbon atoms and hydrogen atoms, examples of the linking group include -O- and -S-. _{, -SO 2 -, - CO -} , - COO -, - OCO -, - CONR a - (R a represents a hydrogen atom or an alkyl group having 1 to 6 carbon ^{atoms), - NR a - (R} a is , And the same meaning as described above) are included, and one kind or two or more kinds may be included. The linking position of the linking group is arbitrary, and for example, it can be located at the end of the divalent hydrocarbon group or between the C-C bonds, but is preferably at one end or between the C-C bonds. Further, the divalent hydrocarbon group and the linking group may be bonded to each other to form a ring structure. The carbon number in paragraph [0030] means the total carbon number of the portion excluding the carbon atoms constituting the linking group.

Specific examples of the divalent hydrocarbon group having the linkage group between the C-C bond, _{e.g., -CH 2 -CH 2 -CH 2 -COO} -CH 2 -CH 2 -, - CH 2 -CH ( _{-CH 3) -CH 2 -COO-CH} 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -OCO-CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -CH 2 -COO _{-CH 2 -CH (CH 2 -CH 3} ) -CH 2 -CH 2 -CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -O-CH 2 -CH (CH 2 -CH 3) - _{CH 2 -CH 2 -CH 2 -CH 2} -, - (CH 2) 5 -COO- (CH 2) 11 -CH 2 -, - CH 2 -CH 2 -CH 2 -C- (COO-CH 2 - _{CH 3) 2 -, - CH} 2 -CH 2 -O-CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -O-CH 2 -CH 2 -, - (CH 2 -CH 2 -O ) _P − CH ₂ - (p is an integer from 1 to _{8), - (CH 2 -CH 2} -CH 2 -O) q -CH 2 - (q is an integer of 1 to 5), - CH ₂ -CH _{(CH 3) -O-CH 2} -CH 2 -, - CH 2 -CH- (OCH 3) -, - CH 2 -CH 2 -COO-CH 2 -CH 2 -O-CH 2 -CH (CH 2 _{-CH 3) -CH 2 -CH 2 -CH} 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -O-CO-CH 2 -CH (CH 2 -CH 3) -CH 2 -CH 2 - _{CH 2 -CH 2 -, - CH} 2 -CH 2 -COO-CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH (CH 2 -CH 3) -CH 2 -CH 2 - _{CH 2 -CH 2 -, - CH} 2 -CH 2 -NH-COO-CH 2 -CH 2 -, - CH 2 -CH 2 -OCO-CH 2 - it is and the like, are limited to Also Not.

  Specific examples of the group having a ring structure formed by combining a divalent hydrocarbon group and the linking group include, but are not limited to, the followings.

  Examples of the substituent of the divalent hydrocarbon group include a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkoxyl group, and a substituted or unsubstituted aryloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkoxyl group may be in the form of straight chain or branched chain, and preferably has 1 to 6 carbon atoms. Specific examples include, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. The aryloxy group is preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof include a phenoxy group and a benzyloxy group. Further, examples of the substituent of the alkoxyl group and the aryloxy group include a halogen atom, a nitro group, a hydroxyl group, an amino group, a carboxyl group and a sulfanyl group. Furthermore, when the divalent hydrocarbon group is a divalent alicyclic hydrocarbon group and a divalent aromatic hydrocarbon group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group is used as a substituent. May have. The alkyl group and the alkenyl group preferably have 1 to 6 carbon atoms. Specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a hexyl group, and the like. Examples include, for example, ethenyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 2-ethyl-2-butenyl group and the like. In addition, as the substituents of the alkyl group and the alkenyl group, the same substituents as the above-mentioned substituents of the divalent hydrocarbon group can be exemplified.

D ¹ represents a dye residue, for example, xanthene dye, triarylmethane dye, cyanine dye, anthraquinone dye, azo dye, dipyrromethene dye, quinophthalone dye, coumarin dye, pyrazolone dye, quinoline. There may be mentioned a residue of a dye selected from a series dye, a nitro series dye, a quinonimine series dye, and a phthalocyanine series dye. Among them, the dye residue is preferably a residue of a dye selected from triarylmethane dyes, xanthene dyes, azo dyes, dipyrromethene dyes, methine dyes, and cyanine dyes, and triarylmethane dyes. A residue of a dye selected from a xanthene dye, a dipyrromethene dye and a cyanine dye is more preferable, and a residue of a triarylmethane dye is further preferable. The dye residue may be derived from any of acid dyes, basic dyes and nonionic dyes, but acid dyes and basic dyes are preferred.

The method for synthesizing the dye monomer is not particularly limited, and a conventionally known method can be used. For example, in the compound represented by the above formula (2), a group having an ethylenically unsaturated group is introduced into the basic skeleton of the dye having a functional group by a general organic synthesis method, or a compound as a raw material for synthesizing the dye. It can be obtained by introducing a group having an ethylenically unsaturated group and then synthesizing a dye. More specifically, the descriptions in JP 2013-178478 A, JP 2013-173850 A, JP 2013-210621 A, JP 2013-028764 A, etc. can be referred to.
And a dye multimer can be manufactured by polymerizing a dye monomer. A conventionally known method can be used for the polymerization reaction, and for example, a method similar to that of the (B) binder resin described later can be adopted.

The dye multimer in the present invention has a polystyrene-equivalent weight average molecular weight (Mw) of 1,000 to 100,000, which is measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran). It is preferably 3,000 to 50,000, more preferably 3,000 to 30,000. With such a mode, heat resistance, solvent resistance, and developability can be achieved in a good balance and at a higher level.
The ratio (Mw / Mn) of the weight average molecular weight (Mw) of the binder resin to the number average molecular weight (Mn) of the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3 .0. In addition, Mn here means the polystyrene equivalent number average molecular weight measured by GPC (elution solvent: tetrahydrofuran).

  The dye multimer may be composed of only the dye monomer, but in view of achieving a high level of heat resistance, solvent resistance and developability, other than the dye monomer. A copolymer having a copolymerizable ethylenically unsaturated monomer (hereinafter, also referred to as “unsaturated monomer (a)”) as a structural unit is preferable. Examples of such unsaturated monomer (a) include, for example, a monomer represented by the following formula (3), an ethylenically unsaturated monomer having one or more carboxyl groups, and N-substituted. Maleimide, an aromatic vinyl compound, vinyl ether, an ethylenically unsaturated monomer having an oxiranyl group or an oxetanyl group, a macromonomer having a mono (meth) acryloyl group at the terminal of the polymer molecular chain, and the like can be mentioned. The unsaturated monomer (a) can be used alone or in combination of two or more.

[In Formula (3),
R ¹² represents a hydrogen atom or a methyl group,
R ¹³ represents an alkanediyl group having 2 to 4 carbon atoms,
R ¹⁴ represents a substituted or unsubstituted hydrocarbon group,
m shows the integer of 0-100. However, when m is 2 or more, a plurality of R ^13's may be the same or different. ]

First, the definition of each symbol in formula (3) will be described.
As R ¹² , a hydrogen atom or a methyl group can be appropriately selected.
Examples of the alkanediyl group having 2 to 4 carbon atoms in R ¹³ include ethylene group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3. -Diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group and the like, among which the number of carbon atoms can be mentioned. 2-3 alkanediyl groups are preferable, and ethylene group and propane-1,2-diyl group are more preferable.

Examples of the hydrocarbon group for R ¹⁴ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
The aliphatic hydrocarbon group may be in the form of a straight chain or a branched chain, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group and an alkynyl group. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group. , Sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group and the like. Further, the alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, preferably an alkenyl group having 2 to 12 carbon atoms, and specific examples thereof include an ethenyl group, a 1-propenyl group, a 1-butenyl group, and 1,3. -Butadienyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-ethyl-2-butenyl group, 2-octenyl group, (4-ethenyl) -5-hexenyl group, 2-decenyl group and the like. Can be mentioned. The alkynyl group is preferably an alkynyl group having 2 to 20 carbon atoms, more preferably an alkynyl group having 2 to 12 carbon atoms, and specific examples thereof include an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a 1-pentynyl group. , 3-pentynyl group, 1-hexynyl group, 2-ethyl-2-butynyl group, 2-octynyl group, (4-ethynyl) -5-hexynyl group, 2-decynyl group and the like. Among them, as the aliphatic hydrocarbon group, a linear or branched alkyl group having 1 to 20 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 12 carbon atoms is preferable.

The alicyclic hydrocarbon group includes a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged ring hydrocarbon group, a spiro hydrocarbon group, a cyclic terpene hydrocarbon group and the like. The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 4 to 30 carbon atoms, more preferably an alicyclic hydrocarbon group having 4 to 18 carbon atoms, and an alicyclic carbon group having 4 to 12 carbon atoms. A hydrogen group is more preferred. Specific examples thereof include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, t-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, tricyclodecanyl group, decahydro-2-naphthyl group, tricyclo [5.2. .1.0 ^2,6 ] Decan-8-yl group, pentacyclopentadecanyl group, isobornyl group, adamantyl group, dicyclopentanyl group, dicyclopentenyl group, tricyclopentanyl group, tricyclopentenyl group, etc. Can be mentioned.

  As the aromatic hydrocarbon group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable. Here, in the present specification, the “aryl group” refers to a monocyclic to tricyclic aromatic hydrocarbon group, and specific examples include, for example, a phenyl group, a benzyl group, an o-tolyl group, and an m-tolyl group. , P-tolyl group, xylyl group, naphthyl group, anthryl group, phenanthryl group, azulenyl group, 9-fluorenyl group and the like.

Examples of the substituent of the hydrocarbon group include a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, a substituted or unsubstituted alkoxy group and the like. When R ¹⁴ is an alicyclic hydrocarbon group or an aromatic hydrocarbon group, it may have a substituted or unsubstituted alkyl group as a substituent. The alkyl group may be in the form of either a straight chain or a branched chain, and preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. The alkoxyl group may be in the form of either a straight chain or a branched chain, and preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms. Specific examples of the halogen atom, the alkyl group, and the alkoxy group are the same as the above-mentioned divalent hydrocarbon group. Further, examples of the substituent of the alkyl group and the alkoxyl group include a halogen atom, a hydroxyl group, a nitro group, an amino group and a cyano group. The position and number of the substituents are arbitrary, and when two or more substituents are included, the substituents may be the same or different.

Among them, the hydrocarbon group for R ¹⁴ is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, more preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 10 carbon atoms.

Although m represents an integer of 0 to 100, m may be 0 or may not have an R ¹³ O group. When it has a R ¹³ O group, m is preferably an integer of 1 to 30, more preferably an integer of 1 to 15, still more preferably an integer of 1 to 10, and still more preferably an integer of 1 to 5. When m is 2 or more, a plurality of R ^13's may be the same or different, and a plurality of R ¹³ O groups may be bonded in any order. Examples of a plurality of different R ^13's include, for example, a combination of an alkanediyl group having 2 carbon atoms and an alkanediyl group having 3 carbon atoms, an alkanediyl group having 2 carbon atoms, and an alkanediyl group having 3 carbon atoms. And a C4 alkanediyl group. Among them, a combination of an ethylene group and a propane-1,2-diyl group, a combination of an ethylene group and a propane-1,3-diyl group, an ethylene group, a propane-1,2-diyl group, and a butane-1, A combination with a 4-diyl group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group are preferable.

Specific examples of the monomer represented by the following formula (3) include:
Alkyl (meth) acrylates such as methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and the like;
Alkenyl (meth) acrylates such as vinyl (meth) acrylate and allyl (meth) acrylate;
Aryl (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate and the like;
Polyethylene glycol (polymerization degree 2-10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2-10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2-10) mono (meth) acrylate, polypropylene (Meth) acrylic acid ester of polyhydric alcohol such as glycol (degree of polymerization 2-10) mono (meth) acrylate, glycerol mono (meth) acrylate;
Alicyclic hydrocarbon groups such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate (Meth) acrylic acid ester having

Examples of the ethylenically unsaturated monomer having one or more carboxyl groups include (meth) acrylic acid, maleic acid, maleic anhydride, monosuccinic acid [2- (meth) acryloyloxyethyl], ω- Examples thereof include carboxypolycaprolactone mono (meth) acrylate and p-vinylbenzoic acid.
Examples of the N-substituted maleimide include N-phenylmaleimide and N-cyclohexylmaleimide.
Examples of aromatic vinyl compounds include styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, and acenaphthylene.
Examples of vinyl ethers include cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, and the like.

Examples of the ethylenically unsaturated monomer having an oxiranyl group include, for example,
Glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, 2,3-bis An ethylenically unsaturated monomer having a glycidyl ether group such as (glycidyloxymethyl) styrene and 2,3,4-tris (glycidyloxymethyl) styrene;
1,2-epoxy-4-vinylcyclohexane;
3,4-epoxycyclohexylmethyl (meth) acrylate and the like can be mentioned.

Examples of the ethylenically unsaturated monomer having an oxetanyl group include, for example,
A (vinyloxyalkyl) alkyloxetane such as 3- (vinyloxymethyl) -2-methyloxetane, 2- (vinyloxyethyl) -2-methyloxetane;
(Meth) acryloyloxyalkyl oxetane such as 3-[(meth) acryloyloxymethyl] oxetane and 2- [2- (meth) acryloyloxyethyl] oxetane;
[(Meth) acryloyloxyalkyl] alkyloxetane such as 3-[(meth) acryloyloxymethyl] -2-methyloxetane and 2- [2- (meth) acryloyloxyethyl] -2-ethyloxetane;
[(Meth) acryloyloxyalkyl] phenyloxetane 4- [3- (3-ethyloxetane-3-ylmethoxy) propoxy] styrene, such as 2-[(meth) acryloyloxymethyl] -2-phenyloxetane, 4- [7 Examples thereof include aromatic vinyl compounds having an oxetanyl group such as-(3-ethyloxetan-3-ylmethoxy) heptyloxy] styrene.

  Examples of the macromonomer include macromonomers having a mono (meth) acryloyl group at the terminal of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane. it can.

  Above all, it is preferable to contain the monomer represented by the above formula (3) as the unsaturated monomer (a).

When the dye multimer is a copolymer of the dye monomer and the unsaturated monomer (a), the copolymerization ratio of the dye monomer in the dye multimer is preferably 5 to 30 mol%, It is preferably 10 to 25 mol%, more preferably 10 to 20 mol%.
The copolymerization ratio of the monomer represented by the above formula (3) in the dye multimer is preferably 30 to 85 mol%, more preferably 40 to 80 mol%, and further preferably 50 to 75 mol%. . In this case, when aryl (meth) acrylate is included as the monomer represented by the above formula (3), the copolymerization ratio of aryl (meth) acrylate in the dye multimer is preferably 5 mol% or more and 20 mol or more. %, More preferably 7 to 18 mol%, further preferably 10 to 16 mol%.

  The coloring composition of the present invention may contain a coloring agent other than the dye and the dye multimer. Examples of such other colorants include pigments, and these other colorants may be used alone or in combination of two or more.

  As the pigment, for example, a compound classified as a pigment in a color index (CI; issued by The Society of Dyers and Colorists), that is, a color index (CI) number as shown below is attached. You can list what you have.

C. I. Pigment Red 166, C.I. I. Pigment Red 177, C.I. I. Pigment Red 224, C.I. I. Pigment Red 242, C.I. I. Pigment Red 254, C.I. I. Pigment Red 264 and other red pigments;
C. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59 and other green pigments;
C. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 80 and other blue pigments;
C. I. Pigment Yellow 83, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 179, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 211, C.I. I. Pigment Yellow 215 and other yellow pigments;
C. I. Pigment Orange 38 and other orange pigments;
C. I. Pigment Violet 23 and other purple pigments.

  In addition, the brominated diketopyrrolopyrrole pigment represented by the formula (Ic) of JP-A-2011-523433 can be used as a red pigment. Further, JP 2001-081348 A, JP 2010-026334 A, JP 2010-191304 A, JP 2010-237384 A, JP 2010-237569 A, JP 2011-006602 A, The lake pigments described in JP 2011-145346 A and the like can be mentioned.

  In the present invention, when the pigment is contained as the (A) colorant, the pigment can be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method or a combination thereof. . If desired, the pigment may be used after its particle surface is modified with a resin. Examples of the resin that modifies the particle surface of the pigment include the vehicle resin described in JP-A-2001-108817, and various commercially available pigment dispersion resins. As a method for coating the carbon black surface with a resin, for example, the methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124699 and the like can be adopted. Further, the organic pigment may be used by making primary particles fine by so-called salt milling. As the salt milling method, for example, the method disclosed in Japanese Patent Laid-Open No. 08-179111 can be adopted.

Further, in the present invention, when the pigment (A) contains a pigment, it may further contain at least one kind selected from known dispersants and dispersion aids.
Known dispersants include, for example, urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkylphenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. Examples thereof include dispersants, polyester-based dispersants, (meth) acrylic dispersants, and as commercially available products, for example, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (above, Big Chemie ( (Manufactured by BYK), etc.), (meth) acrylic dispersants, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-17. , Disperbyk-182 (above, manufactured by BYK), urethane dispersants such as Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), polyethyleneimine-based dispersions such as Solsperse 24000 (manufactured by Lubrizol Co., Ltd.) In addition to polyester-based dispersants such as agents, Ajisper PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881 (all manufactured by Ajinomoto Fine-Techno Co., Inc.), BYK-LPN21324 (manufactured by BYK) can be used. it can.

In the present invention, the dispersant may be used alone or in combination of two or more.
In the present invention, the content of the dispersant is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, further preferably 20 to 100 parts by mass, and further preferably 20 to 50 parts by mass with respect to 100 parts by mass of the pigment. Is more preferable.

  Examples of the dispersion aid include pigment derivatives. Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinophthalone.

The content of the colorant (A) is usually 5 to 70% by mass, preferably 5 to 70% by mass in the solid content of the coloring composition, from the viewpoint of achieving a high level of heat resistance, solvent resistance and developability in good balance. It is 60% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 40% by mass. Here, the solid content is a component other than the solvent described below.
The coloring composition of the present invention may contain the dye and the dye multimer alone as the (A) colorant, but when the dye and the pigment are both included as the (A) colorant, the effect of the present invention can be obtained. From the viewpoint of being more enjoyable, the total content of the dye and the dye multimer is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on all the colorants. Incidentally, the coloring composition of the present invention achieves a well-balanced high level of heat resistance, solvent resistance and developability even when the content ratio of the dye and dye multimer to the solid content of the coloring composition is high. As a result, it is possible to form a colored cured film in which the generation of precipitates and foreign matter in the coating film is suppressed. When the dye contains a triarylmethane dye, it contains a combination of a triarylmethane dye and another blue colorant, or contains 55% by mass or more of the triarylmethane dye with respect to the total content of the dye. If so, the effect of the present invention can be more enjoyed.

-(B) Binder resin-
The coloring composition of the present invention has a copolymerization ratio of the specific copolymer as the (B) binder resin, that is, the copolymerization ratio of the ethylenically unsaturated monomer represented by the following formula (1) is 11 mol% or more. It includes a combination (hereinafter, also referred to as a "specific copolymer", but excluding the dye multimer described above).

[In Formula (1),
R ¹ represents a hydrogen atom or a methyl group,
R ² represents an alkanediyl group having 2 to 4 carbon atoms,
R ³ represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted polycyclic aromatic hydrocarbon group, or a substituted or unsubstituted nitrogen-containing alicyclic heterocyclic group,
n shows the integer of 0-100. However, when n is 2 or more, a plurality of R ^{12 s} may be the same or different. ]

As R ¹ , a hydrogen atom or a methyl group can be appropriately selected.
Examples of the alkanediyl group having 2 to 4 carbon atoms in R ² include the same groups as those exemplified in R ¹³ . Among them, an alkanediyl group having 2 to 3 carbon atoms is preferable, and an ethylene group and a propane-1,2-diyl group are more preferable.

Examples of the polycyclic aromatic hydrocarbon group for R ³ include a polynuclear aromatic hydrocarbon group and a condensed aromatic hydrocarbon group. Here, in the present specification, the “polynuclear aromatic hydrocarbon group” is a hydrocarbon group in which two or more aromatic rings composed of carbon and hydrogen exist, and the aromatic rings are bonded to each other by a carbon-carbon bond. The term "polynuclear aromatic hydrocarbon group" includes not only single bonds between aromatic rings but also hydrocarbon groups having an alkanediyl group or the like bonded thereto. Further, the "fused aromatic hydrocarbon group" has two or more aromatic rings composed of carbon and hydrogen, and these aromatic rings share one or more adjacently bonded carbon atoms. Refers to a hydrocarbon group.
2-10 are preferable, as for the number of the aromatic rings which comprise such a polycyclic aromatic hydrocarbon group, 2-7 are more preferable, and 2-5 are still more preferable.
Specific examples of the polynuclear aromatic hydrocarbon group include, for example, biphenyl group, terphenyl group, quaterphenyl group, kink phenyl group, sexiphenyl group, septiphenyl group, octiphenyl group, nobiphenyl group, deciphenyl group, benzylphenyl group. , Phenethylphenyl group and the like. Of these, a biphenyl group and a benzylphenyl group are preferable.
Specific examples of the condensed aromatic hydrocarbon group include a naphthyl group, anthranyl group, pyrenyl group, phenanthrenyl group, perylenyl group, fluorenyl group and the like. Among them, a naphthyl group, anthranyl group and a fluorenyl group are preferable, and a naphthyl group is more preferable.

The nitrogen-containing alicyclic heterocyclic group for R ³ may be monocyclic or polycyclic, but among them, monocyclic is preferable, and 5- to 7-membered ring is more preferable.
Specific examples of the nitrogen-containing alicyclic heterocyclic group include a pyrrolidinyl group, an imidazolidinyl group, a pyrazolidinyl group, a morpholinyl group, a thiomorpholinyl group, a piperidyl group, a piperidino group, a piperazinyl group, and a homopiperazinyl group. Of these, a piperidyl group is preferable.

  The substituents on the phenyl group, polycyclic aromatic hydrocarbon group and nitrogen-containing alicyclic heterocyclic group include halogen atom, hydroxyl group, nitro group, amino group, cyano group, substituted or unsubstituted alkyl group, substituted or An unsubstituted alkoxy group etc. can be mentioned. The alkyl group may be in the form of a straight chain or a branched chain, and preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and further preferably 1 to 10 carbon atoms. The alkoxyl group may be in the form of a straight chain or a branched chain, and preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms. Specific examples of the halogen atom, the alkyl group and the alkoxy group are the same as those exemplified above. Further, examples of the substituent of the alkyl group and the alkoxyl group include a halogen atom, a hydroxyl group, a nitro group, an amino group and a cyano group. The position and number of the substituents are arbitrary, and when two or more substituents are included, the substituents may be the same or different.

  Moreover, when the substituent of the phenyl group and the polycyclic aromatic hydrocarbon group is a hydroxyl group, the hydroxyl group may be protected. Examples of the protecting group for the hydroxyl group include an ether protecting group, an acetal protecting group, an acyl protecting group, an alkoxycarbonyl group, and a silyl ether protecting group, which can be appropriately selected. Examples of the ether protecting group include a methyl group, benzyl group, methoxybenzyl group and tert-butyl group, and examples of the acyl protecting group include an acetyl group, pivaloyl group and benzoyl group, and an alkoxycarbonyl group. Examples thereof include an ethoxycarbonyl group, a phenoxycarbonyl group, and a tert-butyloxycarbonyl group. Examples of the silyl ether protecting group include a trimethylsilyl group and a tert-butyldimethylsilyl group. In addition, examples of the acetal protecting group include a methoxymethyl group, an ethoxyethyl group, a tetrahydropyranyl group, and tetrahydrofuranyl. Among them, as the hydroxyl-protecting group, an acetal-protecting group is preferable from the viewpoint of heat resistance, solvent resistance and developability. A known method can be adopted as a method for introducing a protecting group into the hydroxyl group.

Among them, R ³ is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted polynuclear aromatic hydrocarbon group, a substituted or unsubstituted nitrogen-containing alicyclic heterocyclic group, and a substituted or unsubstituted phenyl group , A substituted or unsubstituted biphenyl group, a substituted or unsubstituted piperidyl group is more preferable, a phenyl group optionally substituted with a hydroxyl group, a biphenyl group optionally substituted with a hydroxyl group, a hydroxyl group and an alkyl group An optionally substituted benzylphenyl group and a substituted piperidyl group are more preferable. The hydroxyl group may be protected with a protecting group.

Although n represents an integer of 1 to 100, n may be 0 or may not have an R ² O group. When it has a R ² O group, n is preferably an integer of 1 to 30, more preferably an integer of 1 to 15, even more preferably an integer of 1 to 10, and still more preferably an integer of 1 to 5. When n is 2 or more, a plurality of R ^{2 s that} are present may be the same or different, and a plurality of R ² O groups that are present may be bonded in any order. Among them, n is preferably 0 from the viewpoint of achieving a good balance of heat resistance, solvent resistance and developability and achieving a higher level.

  The binder resin (B) may be composed of only the ethylenically unsaturated monomer represented by the formula (1), but from the viewpoint of developability, the ethylenic unsaturated monomer represented by the formula (1) may be used. A copolymer having a copolymerizable ethylenically unsaturated monomer other than the saturated monomer (hereinafter, also referred to as “unsaturated monomer (b)”) as a structural unit is preferable. Examples of such unsaturated monomers (b) include alkyl (meth) acrylates, alkenyl (meth) acrylates, (meth) acrylic acid esters of polyhydric alcohols, and (meth) containing alicyclic hydrocarbon groups. Acrylic ester, ethylenically unsaturated monomer having one or more carboxyl groups, N-substituted maleimide, aromatic vinyl compound, vinyl ether, ethylenically unsaturated monomer having oxiranyl group or oxetanyl group, polymer molecule Examples thereof include macromonomers having a mono (meth) acryloyl group at the chain end. Specific examples of these monomers are the same as those exemplified for the unsaturated monomer (a). The unsaturated monomer (b) can be used alone or in combination of two or more.

Among them, the unsaturated monomer (b) preferably contains an ethylenically unsaturated monomer having one or more carboxyl groups from the viewpoint of developability.
The other monomer preferably contains one or more selected from alkyl (meth) acrylates, N-substituted maleimides and aromatic vinyl compounds.

The copolymerization ratio of the ethylenically unsaturated monomer represented by the formula (1) in the binder resin (B) is 11 mol% or more in all structural units, but the heat resistance and the solvent resistance are further improved. From the viewpoint of improving the composition, 14 mol% or more is preferable, 18 mol% or more is more preferable, 22 mol% or more is further preferable, and 60 mol% or less is more preferable from the viewpoint of further developing property and easiness of synthesis. It is preferably 50 mol% or less, more preferably 40 mol% or less. The range of the copolymerization ratio is preferably 11 to 60 mol%, more preferably 14 to 60 mol%, still more preferably 18 to 50 mol%, further preferably 22 to 50 mol%, still more preferably 22 to 50 mol%. It is 40 mol%. In addition, R ³ of the ethylenically unsaturated monomer represented by the formula (1) is a hydroxyl group-substituted phenyl group or a hydroxyl group-substituted polycyclic aromatic hydrocarbon group, and the hydroxyl group is an acetal protecting group. When it is protected with, the copolymerization ratio of the ethylenically unsaturated monomer represented by the formula (1) in the binder resin (B) is necessarily 11 mol% or more in all structural units. The effect of the invention of the present application can be achieved even if it is not necessary, and it is particularly effective in improving heat resistance.
The copolymerization ratio of the ethylenically unsaturated monomer having one or more carboxyl groups in the binder resin (B) is preferably 10 to 50 mol% in all structural units, more preferably 15 to 35 mol%.

  The binder resin in the present invention can be produced by a known method, but is disclosed in, for example, JP-A-2003-222717, JP-A-2006-259680, and WO 2007/029871. The structure, Mw, and Mw / Mn can be controlled by the method.

The binder resin in the present invention has a polystyrene-reduced weight average molecular weight (Mw) measured by GPC (elution solvent: tetrahydrofuran) of usually 1,000 to 100,000, preferably 3,000 to 50,000, and more preferably It is 5,000 to 30,000. With such a mode, the heat resistance, the solvent resistance, and the developability are well balanced, and it is achieved at a higher level, and the generation of dry foreign matter during coating can be suppressed at a high level.
The ratio (Mw / Mn) of the weight average molecular weight (Mw) of the binder resin to the number average molecular weight (Mn) of the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3 .0. In addition, Mn here means the polystyrene equivalent number average molecular weight measured by GPC (elution solvent: tetrahydrofuran).

The coloring composition of the present invention may contain a binder resin other than the above specific copolymer as the (B) binder resin. As such other binder resin, a (co) polymer of the unsaturated monomer (b) is preferable, and an unsaturated monomer (including an ethylenically unsaturated monomer having one or more carboxyl groups ( The copolymer of b) is more preferable.
In the present invention, the binder resin (B) may be used alone or in combination of two or more.
The content of the (B) binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, relative to 100 parts by mass of the (A) colorant. With such a mode, heat resistance, solvent resistance, and developability can be achieved in a good balance and at a higher level.

-(C) Polymerizable compound-
In the present invention, the polymerizable compound means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, and a caprolactone-modified polyfunctional (meth) acrylate. ) Acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting (meth) acrylate having a hydroxyl group with polyfunctional isocyanate, (meth) acrylate having a hydroxyl group and acid anhydride Examples thereof include a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a product.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol; and 3 such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol. An aliphatic polyhydroxy compound having a valence of 3 or more can be mentioned. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol dimethacrylate. Etc. can be mentioned. Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and anhydrides of dibasic acids such as hexahydrophthalic anhydride, pyromellitic anhydride, and biphenyltetracarboxylic acid. Tetrabasic acid dianhydrides such as dianhydride and benzophenone tetracarboxylic acid dianhydride can be mentioned.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include the compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. The alkylene oxide-modified polyfunctional (meth) acrylate is modified with at least one selected from bisphenol A di (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from ethylene oxide and propylene oxide. Isocyanuric acid tri (meth) acrylate, trimethylolpropane tri (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, penta modified with at least one selected from ethylene oxide and propylene oxide Penta modified with at least one selected from erythritol tri (meth) acrylate, ethylene oxide and propylene oxide Dipentaerythritol modified with at least one selected from lithritol tetra (meth) acrylate, ethylene oxide and propylene oxide Dipentaerythritol modified with at least one selected from penta (meth) acrylate, ethylene oxide and propylene oxide Hexa (meth) acrylate and the like can be mentioned.

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, a urea structure, and the like. In addition, a melamine structure and a benzoguanamine structure mean a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine, or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine and N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril, and the like.

  Of these polymerizable compounds, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher valent aliphatic polyhydroxy compound with (meth) acrylic acid, a caprolactone-modified polyfunctional (meth) acrylate, a polyfunctional urethane (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N ′ -Tetra (alkoxymethyl) benzoguanamine is preferred. Among polyfunctional (meth) acrylates obtained by reacting a trivalent or more aliphatic polyhydroxy compound with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate is a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride among polyfunctional (meth) acrylates having a carboxyl group, and is obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride. The compound is particularly preferable in that it can achieve heat resistance, solvent resistance and developability in a well-balanced manner and at a higher level.

In the present invention, the polymerizable compound (C) may be used alone or in combination of two or more.
The content of the (C) polymerizable compound is preferably 10 to 1,000 parts by mass, more preferably 15 to 500 parts by mass, and still more preferably 20 to 150 parts by mass, relative to 100 parts by mass of the (A) colorant. .. With such a mode, heat resistance, solvent resistance, and developability can be achieved in a good balance and at a higher level.

-(D) Photopolymerization initiator-
The colored composition of the present invention may contain a photopolymerization initiator. This makes it possible to impart radiation sensitivity to the colored composition. The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating the polymerization of the polymerizable compound upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam and X-ray.

  Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, Examples thereof include diazo compounds and imidosulfonate compounds.

  In the present invention, the photopolymerization initiator may be used alone or in combination of two or more. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds and O-acyl oxime compounds.

  Among the preferred photopolymerization initiators in the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, and 2. 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like can be mentioned.

  Further, specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholine. Examples thereof include rinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

  Further, specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis. (2,4-Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4' , 5,5'-tetraphenyl-1,2'-biimidazole and the like.

  When a biimidazole compound is used as the photopolymerization initiator, it is preferable to use a hydrogen donor in combination because the sensitivity can be improved. The "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone. Mention may be made of amine hydrogen donors. In the present invention, the hydrogen donor may be used alone or in combination of two or more, but one or more mercaptan hydrogen donor and one or more amine hydrogen donor are used in combination. Are preferable because the sensitivity can be further improved.

  Further, specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, and 2- [2- ( 5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy) And a triazine compound having a halomethyl group such as tyryl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine. Can be mentioned.

  Further, specific examples of the O-acyl oxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) ) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-). Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like can be mentioned. As a commercially available O-acyl oxime compound, NCI-831, NCI-930 (above, manufactured by ADEKA CORPORATION), OXE-03, OXE-04 (above, manufactured by BASF Corporation) and the like can also be used.

  In the present invention, when a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound is used, a sensitizer can be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  In the present invention, the content of the (D) photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, and 5 to 100 parts by mass of the (C) polymerizable compound. 50 parts by mass is more preferable. By adopting such an embodiment, the heat resistance, the solvent resistance and the developability are well balanced and a higher level is achieved, so that the curability and the coating property can be further enhanced.

-(E) Solvent-
The coloring composition of the present invention contains the above-mentioned components (A) to (C) and optionally other components, and is usually prepared as a liquid composition by mixing an organic solvent. .
As the solvent (E), as long as it is a solvent that disperses or dissolves the components (A) to (C) and other components constituting the coloring composition, does not react with these components, and has appropriate volatility. , Can be appropriately selected and used.

Among such organic solvents, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, (poly) alkylene glycol monoalkyl ethers such as tripropylene glycol monoethyl ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetate such as 3-methyl-3-methoxybutyl acetate;
Glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether;
Cyclic ethers such as tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate and 1,6-hexanediol diacetate;
Alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutylpropionate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyrate Fatty acid alkyl esters such as propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, and lactams.

  Among these organic solvents, one or more selected from (poly) alkylene glycol monoalkyl ether acetates, keto alcohols and ketones are preferable from the viewpoint of solubility, pigment dispersibility, coatability and the like.

In the present invention, the solvent may be used alone or in combination of two or more.
The content of the (E) solvent is not particularly limited, but the total concentration of each component excluding the solvent of the coloring composition is preferably 5 to 50% by mass, and 10 to 40% by mass. Amounts are more preferred. By adopting such an embodiment, dispersibility and stability are enhanced, and therefore heat resistance, solvent resistance, and developability can be achieved in a good balance and at a higher level.

-Additive-
The coloring composition of the present invention may contain various additives, if necessary.
Examples of the additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorine-based surfactants and silicone-based surfactants; vinyl. Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropro Adhesion promoters such as rutrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di- t-Butylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-t-butyl-4-hydroxy) -5-Methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxa-spiro [5.5] undecane, thiodiethylenebis [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate] and the like; 2- (3-t-butyl-5-methyl-2-hydroxy) UV absorbers such as phenyl) -5-chlorobenzotriazole and alkoxybenzophenones; aggregation inhibitors such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol , 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol Residue improvers such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. Examples thereof include improvers.

Method for producing colored composition The colored composition of the present invention comprises, for example, a dye solution obtained by dissolving at least one selected from a dye and a dye multimer as a (A) colorant in a solvent (E), It can be prepared by adding (B) binder resin, (C) polymerizable compound, and further (E) solvent and other components, and mixing. When the coloring composition of the present invention further contains a pigment as the (A) colorant, the pigment is used in the presence of a dispersant in the (E) solvent, optionally with a part of the (B) binder resin, for example, Using a bead mill, a roll mill, etc., it is mixed and dispersed while being pulverized to obtain a pigment dispersion liquid, and then, in this pigment dispersion liquid, at least one selected from (A) dye and dye multimer is added to (E) solvent. Add the dye solution obtained by dissolution, (C) polymerizable compound, (B) binder resin, (D) photopolymerization initiator if necessary, and additional (E) solvent and other components. It can be prepared by mixing. Further, a pigment is mixed and dispersed in a solvent (E) in the presence of a dispersant with at least one selected from a dye (A) and a dye multimer to prepare a dispersion liquid, and then this colorant dispersion liquid is prepared. (C) a polymerizable compound, (B) a binder resin, (D) a photopolymerization initiator if necessary, and further (E) a solvent or other components, and mixing them to prepare the mixture. You can also

Colored cured film and method for forming the same The colored cured film of the present invention is formed by using the colored composition of the present invention, and comprises (A) a dye and a dye having a dye residue and an ethylenically unsaturated group. The colorant containing at least one kind selected from dye multimers having a monomer as a structural unit and (B) the copolymerization ratio of the ethylenically unsaturated monomer represented by the formula (1) is 11 mol%. It contains the above-mentioned copolymer (however, the above-mentioned dye multimer is excluded). Specifically, it means each color pixel, black matrix, black spacer, etc. used in the color filter.

Hereinafter, the colored cured film used for the color filter and the method for forming the same will be described.
As a method of forming the colored cured film that constitutes the color filter, the following method is first mentioned. First, if necessary, a light-shielding layer (black matrix) is formed on the surface of the substrate so as to partition the portions for forming pixels. Then, for example, a red liquid composition of the radiation-sensitive coloring composition of the present invention is applied onto this substrate, followed by prebaking to evaporate the solvent to form a coating film. Next, this coating film is exposed through a photomask and then developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Then, post-baking is performed to form a pixel array in which red pixel patterns (colored cured film) are arranged in a predetermined array.

  Then, using each of the green or blue radiation-sensitive coloring compositions, coating, pre-baking, exposure, development and post-baking of each radiation-sensitive coloring composition is performed in the same manner as described above to obtain a green pixel array and blue. The pixel array of 1 is sequentially formed on the same substrate. As a result, the color filter in which the pixel arrays of the three primary colors of red, green and blue are arranged on the substrate can be obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

  The black matrix can be formed by forming a thin metal film of chromium or the like formed by sputtering or vapor deposition into a desired pattern by using a photolithography method. It can also be formed by using the colorant composition in the same manner as in the case of forming the pixel.

Examples of the substrate used when forming the colored cured film include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
If desired, these substrates may be subjected to appropriate pretreatments such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum vapor deposition and the like.

  When applying the radiation-sensitive coloring composition to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method (slit coating method), or a bar coating method. However, it is particularly preferable to use a spin coating method or a slit die coating method.

  The heating and drying conditions in the pre-baking are usually 70 to 110 ° C. and about 1 to 10 minutes.

  The coating thickness of the cured film of the color filter used for the display device is usually 0.6 to 8 μm, preferably 1.2 to 5 μm as the film thickness after drying. The coating thickness of the cured film of the color filter used in the solid-state imaging device is usually 0.3 to 5 μm, preferably 0.5 to 2 μm as the film thickness after drying.

  Examples of the radiation light source used when forming at least one selected from the pixel and the black matrix include, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure lamp. Examples thereof include a lamp light source such as a mercury lamp and a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. Radiation having a wavelength in the range of 190 to 450 nm is preferable.

Generally, the exposure dose of radiation is preferably 10 to 10,000 J / m ² .
Examples of the alkaline developer include sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene. An aqueous solution of 1,5-diazabicyclo- [4.3.0] -5-nonene or the like is preferable.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. After the alkali development, it is usually washed with water.
As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid pour) development method, or the like can be applied. The developing conditions are preferably room temperature and 5 to 300 seconds.

The post-baking condition is usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is 0.5 to 8 μm, preferably 1 to 4 μm when it is used as a colored cured film of a color filter used for a display element. When it is used as a colored cured film of a color filter used in a solid-state imaging device, it is usually 0.3 to 4 μm, preferably 0.5 to 2 μm.

  In addition, as a second method of forming a colored cured film forming a color filter, a method of obtaining pixels of each color by an inkjet method, which is disclosed in JP-A-7-318723, 2000-310706 and the like. Can be adopted. In this method, first, a partition that also has a light-shielding function is formed on the surface of the substrate. Then, for example, a red liquid composition of the thermosetting coloring composition of the present invention is discharged into the formed partition wall by an inkjet device, and then prebaked to evaporate the solvent. Next, this coating film is exposed if necessary, and then post-baked to cure it, thereby forming a red pixel pattern.

  Then, using each of the green or blue thermosetting coloring compositions, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as above. As a result, a color filter in which pixel patterns of three primary colors of red, green and blue are arranged on the substrate can be obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

Incidentally, the partition wall not only has a light-shielding function, but also has a function of preventing the thermosetting coloring compositions of the respective colors discharged into the compartments from being mixed with each other, so that it is more effective than the black matrix used in the first method described above. , The film thickness is thick. Therefore, the partition wall is usually formed by using the black radiation-sensitive composition.
The substrate and the light source of radiation used when forming the colored cured film, and the prebaking and postbaking methods and conditions are the same as those of the first method described above. In this way, the film thickness of the pixel formed by the inkjet method is approximately the same as the height of the partition wall.

  A protective film is formed on the pixel pattern thus obtained, if necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, spacers may be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but it may be a spacer having a light-shielding property (black spacer). In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used.

  The color filter containing the colored cured film of the present invention thus formed achieves a high level of heat resistance, solvent resistance and developability in a well-balanced manner, and therefore, a color liquid crystal display element, a color image pickup tube element, a color filter It is extremely useful as a sensor, an organic EL display device, electronic paper, a solid-state imaging device, and the like.

Color Filter The color filter of the present invention comprises the colored cured film of the present invention. Specifically, it is sufficient that the colored cured film of the present invention is provided as a member of each color pixel used in a color filter, a black matrix, a black spacer, or the like.

Display Element The display element of the present invention comprises the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, electronic paper and the like.
The color liquid crystal display device provided with the colored cured film of the present invention may be a transmissive type or a reflective type, and can have an appropriate structure. For example, a structure in which a color filter is formed on a substrate different from a driving substrate on which thin film transistors (TFTs) are arranged, and the driving substrate and the substrate on which the color filter is formed face each other with a liquid crystal layer in between. And a substrate on which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is arranged, and a substrate on which an ITO (tin-doped indium oxide) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure in which they face each other. The latter structure has an advantage that the aperture ratio can be significantly improved and a bright and high-definition liquid crystal display device can be obtained. In the case of adopting the latter structure, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed or the substrate side on which the ITO electrode is formed.

  The color liquid crystal display device including the colored cured film of the present invention may include a cold cathode fluorescent tube (CCFL) and a backlight unit using a white LED as a light source. Examples of the white LED include a white LED that obtains white light by mixing colors by combining a red LED, a green LED, and a blue LED, and a white LED that obtains white light by mixing colors by combining a blue LED, a red LED, and a green phosphor, and a blue LED. A white LED that obtains white light by mixing colors of a red-emitting phosphor and a green-emitting phosphor, a white LED that obtains white light by mixing a blue LED and a YAG-based phosphor, a blue LED, an orange-emitting phosphor, and a green-emitting fluorescent Examples thereof include a white LED that obtains white light by mixing colors by combining the bodies, and a white LED that obtains white light by mixing colors by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor and a blue light emitting phosphor.

  The color liquid crystal display device including the colored cured film of the present invention includes a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, an IPS (In-Planes Switching) type, a VA (Vertical Alignment) type, and an OCB (Optical) type. An appropriate liquid crystal mode such as Compensated Birefringence type can be applied.

Further, the organic EL display device including the colored cured film of the present invention can have an appropriate structure, and for example, the structure disclosed in JP-A No. 11-307242 can be mentioned.
In addition, the electronic paper provided with the colored cured film of the present invention can have an appropriate structure, and examples thereof include the structure disclosed in Japanese Patent Laid-Open No. 2007-41169.

Solid-state image sensor The solid-state image sensor of the present invention comprises the colored cured film of the present invention. Moreover, the solid-state imaging device of the present invention can have an appropriate structure. For example, in one embodiment, the colored composition of the present invention is used to form a colored pixel (colored cured film) on a semiconductor substrate such as a CMOS substrate by the same operation as described above, thereby performing color separation. A solid-state imaging device having excellent properties can be manufactured.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Synthesis of colorant>
Colorant synthesis example 1
Dye monomer synthesis Stirrer was placed in a 1 L 3-necked flask previously purged with nitrogen, and 3.36 g (3.67 mmol) of tris (dibenzylideneacetone) -dipalladium (0), (±) -2, 4.58 g (7.36 mmol) of 2'-bis (diphenylphosphino) -1,1'-binaphthyl and 450 mL of 1,2-dimethoxyethane deaerated by nitrogen bubbling in advance were added, and the mixture was heated to 80 ° C under a nitrogen stream. And stirred for 1 hour. Then, the mixture was cooled to 40 ° C. or lower, and 25.0 g (0.260 mol) of sodium t-butoxide, 23.0 g (0.200 mol) of 4-aminocyclohexanol, and 1-sodium while preventing air from entering the system. Bromonaphthalene 38.0 g (0.184 mol) was sequentially added, and the mixture was stirred under reflux for 3 hours. Then, the reaction mixture was cooled to room temperature and filtered through Celite. The filtered Celite was washed with ethyl acetate. The filtrate after the Celite filtration was mixed with a washing liquid obtained by washing Celite with ethyl acetate, and the mixture was concentrated under reduced pressure with a rotary evaporator. The obtained residue was purified by silica gel column chromatography to obtain 33.0 g (0.137 mol, yield 74%) of a viscous solid. This compound is designated as (A1).

  A stirrer was put, and 12.0 g (0.0497 mol) of the above compound (A1), 7.55 g (0.0746 mol) of triethylamine, and 6.07 g of 4-dimethylaminopyridine were placed in a 500-mL three-necked flask that had been previously purged with nitrogen. 0.0497 mol) and 250 mL of ethyl acetate were added, and the internal temperature was cooled to 5 ° C. To this mixture, 6.24 g (0.0259 mol) of methacryloyl chloride was added dropwise so that the internal temperature did not exceed 10 ° C, the internal temperature was raised to room temperature, and the mixture was stirred at the same temperature for 4 hours under a nitrogen stream. Then, the reaction mixture was washed successively with 300 mL of water and 300 mL of saturated saline, the organic layer was dried over anhydrous sodium sulfate, and then concentrated under reduced pressure to 40 g on a rotary evaporator. Then, 200 g of toluene was added and the mixture was concentrated under reduced pressure with a rotary evaporator to 40 g, and 85 g of toluene was added again. To the obtained solution, 4,4'-bis (diethylamino) benzophenone (20.5 g, 0.0633 mol), 4-methoxyphenol (0.100 g) and phosphoryl chloride (8.05 g, 0.0518 mol) were sequentially added at room temperature. The mixture was stirred at 100 ° C. for 2 hours under a nitrogen stream. Then, the reaction mixture was cooled to room temperature and most of the toluene was distilled off under reduced pressure with a rotary evaporator. The obtained residue was dissolved in 500 mL of chloroform and washed with 500 mL of water. The organic layer was concentrated under reduced pressure with a rotary evaporator, and acetone was added to the obtained residue to make the total mass 400 g. The solution obtained here was added dropwise to 3200 g of diisopropyl ether, and the obtained solid was collected by filtration. This solid was dried under reduced pressure at 50 ° C. for 12 hours to obtain 18.0 g (0.0276 mol, yield 56%) of a colored solid. This compound is designated as (A2).

  Into a 100 mL Erlenmeyer flask containing a stir bar, 9.00 g (13.8 mmol) of the above compound (A2) and 5.94 g (20.7 mmol) of bis (trifluoromethanesulfonyl) imide lithium were charged, and 90 mL of ethyl acetate, ion-exchanged water. 90 mL was added and stirred at room temperature for about 2 hours. After that, the aqueous layer was separated and removed, and the organic layer was washed 3 times with 100 mL of ion-exchanged water. The organic layer was concentrated under reduced pressure, and the residue was dried under reduced pressure at 50 ° C. for 12 hours to obtain 11.4 g (12.7 mmol, yield 92%) of a compound represented by the following formula (A3). This is designated as compound (A3).

Synthetic stirrer of dye multimer was put, 100 mL three-necked flask equipped with a reflux condenser and a thermometer was sufficiently replaced with nitrogen, and 15.0 g of cyclohexanone was charged, and heated to an internal temperature of 70 ± 2 ° C. under a nitrogen stream. did. On the other hand, 9.0 g (10.0 mmol) of compound (A3), 1.0 g (11.6 mmol) of methacrylic acid, 5.0 g (50.0 mmol) of methyl methacrylate, and 2,2 which are polymerization initiators. A solution prepared by mixing 2.02 g (8.13 mmol) of 4'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, trade name V-65) and 45.0 g of cyclohexanone was used. The temperature was kept at ± 2 ° C, and the mixture was added dropwise using a pump over 2 hours. After the dropwise addition was completed, stirring was continued for another hour at the same temperature. Thereafter, 0.728 g (2.71 mmol) of 2,2′-azobis (2,4-dimethylvaleronitrile) dissolved in 1.16 g of cyclohexanone was added to the reaction mixture at once and stirred at the same temperature for 3 hours. . The reaction solution was cooled to room temperature and added dropwise to a large amount of hexane. The colored solid obtained was dried under reduced pressure at 50 ° C. to obtain 14.4 g (yield 96%) of a copolymer. The obtained copolymer had Mw of 5,300. Let this polymer be a coloring agent (A-1).

Colorant Synthesis Examples 2-3
In the “Synthesis of Dye Multimer” of Colorant Synthesis Example 1, the polymer (A- 2) to (A-3) were synthesized. The obtained copolymers are designated as colorants (A-2) to (A-3), respectively.

<Synthesis of binder resin>
Binder resin synthesis example 1
A flask equipped with a cooling tube and a stirrer was charged with 29 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. After heating to 80 ° C., at the same temperature, propylene glycol monomethyl ether acetate 30.85 parts by mass, methacrylic acid 6.06 parts by mass (70.4 mmol), methyl methacrylate 16.67 parts by mass (166.5 mmol), phenyl methacrylate. A mixed solution of 15.15 parts by mass (93.4 mmol) and 2.27 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added dropwise over 1 hour, and the temperature was maintained at 2 Polymerized for hours. Then, the temperature of the reaction solution was raised to 100 ° C., and polymerization was further performed for 1 hour to obtain a solution containing the binder resin (B1) (solid content concentration 40% by mass). This is referred to as "binder resin (B1) solution". The binder resin (B1) obtained had Mw of 9,700 and Mn of 4,800.

Binder resin synthesis examples 2 to 21
A binder resin solution (solid content concentration 40% by mass) was obtained in the same manner as in Binder Resin Synthesis Example 1 except that the raw materials used were changed as shown in Table 2. These resin solutions are referred to as “binder resin (B2) solution” to “binder resin (B21) solution”. The binder resins (B1) to (B10), the binder resins (B12) to (B16) and the binder resins (B18) to (B20) correspond to the specific copolymer, and the binder resin (B11), the binder resin (B17) and The binder resin (B21) does not correspond to the specific copolymer. In Table 2, as the "acetal-protected 4-hydroxyphenylmethacrylate", one synthesized by the method described below was used. Table 2 shows raw materials used in units of mmol.

<Synthesis of 4-hydroxyphenylmethacrylate protected acetal>
Synthesis example 1
150 mL of dichloromethane, 10 g (56.1 mmol) of 4-hydroxyphenyl methacrylate and 1.41 g (5.61 mmol) of pyridinium paratoluenesulfonate were charged into a two-necked flask containing a stirrer and stirred, and then at room temperature. 6.07 g (84.2 mmol) of ethyl vinyl ether was added dropwise over 15 minutes. After completion of the dropping, the mixture was further stirred at room temperature for 3 hours to sufficiently react. After completion of the reaction, the mixture was extracted with diethyl ether, washed with 1M aqueous sodium hydroxide solution, and then dried over magnesium sulfate. The white solid obtained after removing the solvent was purified by a silica gel column to obtain 11.2 g (44.9 mmol, yield 80%) of an acetal-protected 4-hydroxyphenylmethacrylate.

<Preparation of colorant solution>
Preparation example 1
10 parts by mass of the colorant (A-1) obtained above was dissolved in 90 parts by mass of propylene glycol monomethyl ether to obtain a colorant solution (A-1).

Preparation Examples 2-9
In Preparation Example 1, the types and amounts of the colorant and solvent used were changed as shown in Table 3 to obtain colorant solutions (A-2) to (A-9). In Table 3, "dipyrromethene dye 1" means Exemplified Compound III-1 described in Chemical Formula 54 of Japanese Patent No. 5085256, and "PGME" means propylene glycol monomethyl ether.

Preparation Example 10
As a colorant, C.I. I. Pigment Blue 15: 6 (15 parts by mass), BYK-LPN21116 (manufactured by BYK Corporation) as a dispersant (12.5 parts by mass) (solid content concentration 40% by mass), and C.I. I. 0.5 parts by mass of Solvent Blue, 12.5 parts by mass of binder resin (B2) solution (concentration of solid content: 40% by mass), and 59.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent were treated with a bead mill. Thus, a pigment dispersion liquid (A-10) was prepared.

Preparation Examples 11 to 17
In Preparation Example 10, the types of pigment and binder resin solution used were changed as shown in Table 4 to obtain pigment dispersions (A-11) to (A-17).

<Preparation and evaluation of coloring composition>
Example 1
(A) 33.0 parts by mass of the colorant solution (A-1) as the colorant, (B) 11.9 parts by mass of the binder resin (B1) solution as the binder resin (solid content concentration 40% by mass), (C) polymerization 7.2 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as the photoactive compound, and NCI-930 (made by ADEKA Co., Ltd.) as a photopolymerization initiator. ) 0.6 parts by mass, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole 0.3 parts by mass, 2,4-diethyl 0.2 parts by mass of thioxanthone and 0.2 parts by mass of 2-mercaptobenzothiazole, Megafac F-554 (manufactured by DIC Corporation) as a fluorochemical surfactant. .03 parts by weight and 29.9 parts by mass of propylene glycol monomethyl ether acetate and a mixture of diacetone alcohol 16.7 parts by weight solvent, and blue colored composition (BS-1) was prepared.

Evaluation of heat resistance The coloring composition (BS-1) was applied on a soda glass substrate on the surface of which a SiO ₂ film for preventing elution of sodium ions was formed using a spin coater, and then a hot plate at 90 ° C. Was pre-baked for 2 minutes to form a coating film having a film thickness of 2.5 μm.
Then, after cooling this substrate to room temperature, the coating film was exposed to radiation having wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 400 J / m ² through a photomask using a high-pressure mercury lamp. After that, shower development was performed on these substrates for 60 seconds by discharging a developer consisting of 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm). . Then, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230 ° C. for 20 minutes to form a colored cured film on the substrate.
With respect to the obtained colored cured film, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), a C light source, a two-degree visual field, chromaticity coordinate values (x, y) and stimulus values (Y) in a CIE color system. ) Was measured.
Then, the substrate was additionally baked twice at 230 ° C. for 20 minutes. The chromaticity coordinate values (x, y) and the stimulus value (Y) of the substrate after the additional baking was performed twice were measured, and the color change before and after the additional baking of two times, that is, ΔE ^* ab was evaluated. As a result, when the value of ΔE ^* ab is 1.0 or less, it is “◎”, when it is more than 1.0 and 2.0 or less, it is “◯”, and when it is more than 2.0 and 3.0 or less, it is “Δ”. , And the case of larger than 3.0 was evaluated as “x”. It can be said that the smaller the ΔE ^* ab value, the better the heat resistance.

Evaluation of solvent resistance The coloring composition (BS-1) was applied on a soda glass substrate having a SiO ₂ film which prevents elution of sodium ions on the surface using a spin coater, and then hot at 90 ° C. The plate was prebaked for 2 minutes to form a coating film having a film thickness of 2.5 μm.
Then, after cooling this substrate to room temperature, the coating film was exposed to radiation having wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 400 J / m ² through a photomask using a high-pressure mercury lamp. After that, shower development was performed on these substrates for 60 seconds by discharging a developer consisting of 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm). . After that, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230 ° C. for 20 minutes to form a strip-shaped pattern on the substrate. Then, the substrate was immersed in a mixed solution of N-methylpyrrolidone: butyl cellosolve = 50: 50 (volume ratio) at 80 ° C. for 5 minutes.
The chromaticity coordinate values (x, y) and the stimulus value (Y) were measured before and after the immersion, and the color change before and after the immersion, that is, ΔE ^* ab was evaluated. When the value of ΔE ^* ab is 1.0 or less, it is “◎”, when it is more than 1.0 and 2.0 or less, it is “◯”, and when it is more than 2.0 and 3.0 or less, it is “Δ”, 3 The case where it was larger than 0.0 was evaluated as "x". It can be said that the smaller the ΔE ^* ab value, the better the solvent resistance.

Evaluation of developability The coloring composition (BS-1) was applied using a spin coater on a soda glass substrate on the surface of which a SiO ₂ film that prevents elution of sodium ions was formed, and then a hot plate at 90 ° C. Was pre-baked for 2 minutes to form a coating film having a film thickness of 2.5 μm.
Then, after cooling this substrate to room temperature, the coating film was exposed to radiation having wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 400 J / m ² through a photomask using a high-pressure mercury lamp. After that, shower development was performed on these substrates by discharging a developing solution containing a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm). At this time, the time (BP) until the film in the unexposed portion disappeared and the substrate surface was visible was evaluated. B. P. Is within 30 seconds, "○", over 30 seconds and within 40 seconds is "○", over 40 seconds and within 50 seconds is "△", over 50 seconds is "x". Evaluated as.

Examples 2-21 and Comparative Examples 1-3
In Example 1, the same operations as in Example 1 were carried out except that the types of the colorant solution and the binder resin solution used were changed as shown in Tables 5 and 6, and the blue coloring compositions (BS-2) to (BS). -24) was prepared and evaluated in the same manner as in Example 1. Table 5 shows the evaluation results of Examples 2 to 10, and Table 6 shows the evaluation results of Examples 11 to 21 and Comparative Examples 1 to 3, respectively.

In Tables 5 and 6, each component is as follows.
C-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA)
D-1: NCI-930 (made by ADEKA Corporation)
D-2: 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole D-3: 2,4-diethylthioxanthone D-4: 2-Mercaptobenzothiazole F-1: Megafac F-554 (manufactured by DIC Corporation)
E-1: Propylene glycol monomethyl ether acetate E-2: Diacetone alcohol E-3: Cyclohexanone

Example 22
(A) 27.2 parts by mass of the colorant solution (A-2) and 6.1 parts by mass of the pigment dispersion liquid (A-13) as the colorant, 10.6 parts by mass of the binder resin (B2) solution (solid content concentration 40 Mass%), (C) 6.8 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a polymerizable compound, and NCI as a photopolymerization initiator. -930 (manufactured by ADEKA CORPORATION) 0.6 parts by mass, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole 0.3 Parts by mass, 0.2 parts by mass of 2,4-diethylthioxanthone and 0.2 parts by mass of 2-mercaptobenzothiazole, and Megafac F-554 (DI as a fluorosurfactant. (Manufactured by K.K.) 0.03 parts by mass, and 31.4 parts by mass of propylene glycol monomethyl ether acetate as a solvent and 16.7 parts by mass of diacetone alcohol were mixed to prepare a blue colored composition (BS-25). .
Using the prepared coloring composition (BS-25), evaluation was carried out in the same manner as in Example 1. The results are shown in Table 7.

Examples 23-25 and Comparative Examples 4-6
A blue coloring composition (BS-26) was prepared in the same manner as in Example 22 except that the types of the colorant solution, pigment dispersion and binder resin solution used in Example 22 were changed as shown in Table 7. (BS-31) was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 7.

In Table 7, each component is as follows.
C-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA)
D-1: NCI-930 (made by ADEKA Corporation)
D-2: 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole D-3: 2,4-diethylthioxanthone D-4: 2-Mercaptobenzothiazole F-1: Megafac F-554 (manufactured by DIC Corporation)
E-1: Propylene glycol monomethyl ether acetate E-2: Diacetone alcohol E-3: Cyclohexanone

Example 26
(A) Pigment dispersion (A-10) 18.7 parts by mass as a colorant and colorant solution (A-5) 9.9 parts by mass, (B) Binder resin (B2) solution 14.1 parts by mass as a binder resin. Parts (solid content concentration 40% by mass), (C) 7.0 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a polymerizable compound, 0.5 parts by mass of NCI-930 (manufactured by ADEKA CORPORATION) as a photopolymerization initiator, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2 ′ -Biimidazole 0.04 parts by mass, 2,4-diethylthioxanthone 0.02 parts by mass, 2-mercaptobenzothiazole 0.02 parts by mass, and a fluorosurfactant. And Megafac F-554 (manufactured by DIC Corporation) 0.03 parts by mass, and 35.8 parts by mass of propylene glycol monomethyl ether acetate and 16.7 parts by mass of diacetone alcohol as a solvent, to obtain a blue colored composition. (BS-32) was prepared.
Evaluation was performed in the same manner as in Example 1 using the prepared coloring composition (BS-32). The results are shown in Table 8.

Examples 27-31 and Comparative Examples 7-11
In Example 26, the type and amount of each component used was changed as shown in Table 8 to prepare a coloring composition. Then, the prepared coloring composition was used and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 8. The coloring compositions (BS-32) to (BS-36) are blue, the coloring compositions (RS-1) to (RS-4) are red, and the coloring compositions (GS-1) to (GS-2). Is a green composition.

In Table 8, each component is as follows.
C-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA)
D-1: NCI-930 (made by ADEKA Corporation)
D-2: 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole D-3: 2,4-diethylthioxanthone D-4: 2-Mercaptobenzothiazole F-1: Megafac F-554 (manufactured by DIC Corporation)
E-1: Propylene glycol monomethyl ether acetate E-2: Diacetone alcohol E-3: Cyclohexanone

Claims (11)

(A) a colorant containing at least one selected from a dye and a dye multimer having a dye monomer having a dye residue and an ethylenically unsaturated group as a structural unit,
(B) a binder resin, and (C) a polymerizable compound,
As the binder resin (B), a copolymer having a copolymerization ratio of the ethylenically unsaturated monomer represented by the following formula (1) of 11 mol% or more (excluding the dye multimer) is contained. A coloring composition for a color filter .

[In Formula (1),
R ¹ represents a hydrogen atom or a methyl group,
R ² represents an alkanediyl group having 2 to 4 carbon atoms,
R ³ is a substituted or unsubstituted phenyl group, a substituted or unsubstituted polycyclic aromatic hydrocarbon group, or a substituted or unsubstituted nitrogen-containing alicyclic heterocyclic group , which is a polycyclic aromatic hydrocarbon group. Is biphenyl group, terphenyl group, quaterphenyl group, kink phenyl group, sexiphenyl group, septiphenyl group, octiphenyl group, nobiphenyl group, deciphenyl group, benzylphenyl group, phenethylphenyl group, naphthyl group, anthranyl group, pyrenyl group A phenanthrenyl group, a perylenyl group, or a fluorenyl group, wherein the nitrogen-containing alicyclic heterocyclic group is a pyrrolidinyl group, an imidazolidinyl group, a pyrazolidinyl group, a morpholinyl group, a thiomorpholinyl group, a piperidyl group, a piperidino group, a piperazinyl group, or a homopiperazinyl group. Yes, the substituent is a hydroxy group, nit Group, an amino group, a cyano group, an optionally substituted alkyl group, and 1 or 2 or more selected from alkoxy group which may have a substituent,
n represents 0 . ] The coloring composition for a color filter according to claim 1, wherein in the copolymer, the copolymerization ratio of the ethylenically unsaturated monomer represented by the formula (1) is 22 mol% or more. The dye includes a dye selected from triarylmethane dyes, xanthene dyes, dipyrromethene dyes and cyanine dyes, or is selected from triarylmethane dyes, xanthene dyes, dipyrromethene dyes and cyanine dyes. The coloring composition for a color filter according to claim 1, comprising a dye multimer having a dye monomer having a dye residue and an ethylenically unsaturated group as a structural unit. R ³ Is a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted benzylphenyl group, or a substituted or unsubstituted piperidyl group, the substituent is a hydroxy group, a nitro group, an amino group, The cyano group, an alkyl group which may have a substituent, and an alkoxy group which may have a substituent, or 1 or 2 or more thereof, which is any one of claims 1 to 3. Coloring composition for color filter. R ³ Is a phenyl group optionally substituted with a hydroxyl group or an alkoxy group, a biphenyl group optionally substituted with a hydroxyl group, a benzylphenyl group optionally substituted with a hydroxyl group and an alkyl group, or an alkyl group substituted The coloring composition for a color filter according to any one of claims 1 to 4, which is an optionally piperidyl group. In the copolymer, the copolymerization ratio of the ethylenically unsaturated monomer represented by the formula (1) is 60 mol% or less, for a color filter according to any one of claims 1 to 5 Coloring composition. The dye monomer is a monomer represented by the following formula (2), a color filter coloring composition according to any one of claims 1-6.

[In the formula (2),
R ¹¹ represents a hydrogen atom or a methyl group,
X ¹ is a single bond, a substituted or unsubstituted divalent hydrocarbon group, or a combination of the divalent hydrocarbon group and one or more linking groups containing atoms other than carbon atoms and hydrogen atoms 2 Indicates a valence group,
D ¹ represents a dye residue. ] Colored cured film formed using the color filter for coloring composition according to any one of claims 1-7. A color filter comprising the colored cured film according to claim 8 . A display device comprising the colored cured film according to claim 8 . A solid-state imaging device comprising the colored cured film according to claim 8 .