JP2018188488A - Colored composition, colored cured film, and display element and solid-state image sensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored composition from which a colored cured film is formed that has excellent heat resistance and adhesiveness to a substrate and less likely induces foreign substances in a coating film.SOLUTION: The colored composition comprises (A) a colorant, (B) a resin and (C) a polymerizable compound, in which the (B) resin comprises (b1) a polymer having a cationic moiety and an anionic moiety in the same molecule. The (b1) polymer having a cationic moiety and an anionic moiety in the same molecule is preferably a polymer having a repeating unit represented by formula (1). In the formula, Ris H or a methyl group; Rand Rare each independently a divalent organic group; (C)is -NRR-, -PRR-, -OP(=O)(-O-)O, -SONSO- or -C(=O)NSO-, where Rto Rare each independently a monovalent organic group; and (A)is CO, SO, PO, NRRRor PRR.SELECTED DRAWING: None

Description

  The present invention relates to a colored composition, a colored cured film, a display element, and a solid-state image sensor, and more particularly, to a transmissive or reflective color liquid crystal display element, solid-state image sensor, organic EL display element, electronic paper, and the like. The present invention relates to a colored composition suitably used for producing a colored cured film to be used, a colored cured film formed using the colored composition, and a display element and a solid-state imaging device including the colored cured film.

  In manufacturing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. (Hereinafter, referred to as “exposure”) and a method of obtaining pixels of each color by development (Patent Documents 1 and 2) are known. A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed is also known. Furthermore, a method of obtaining pixels of each color by an inkjet method using a pigment-dispersed colored resin composition is also known.

Dyes have been widely studied as colorants used in the production of color filters. This is because when a dye is used as a colorant, the hue and brightness of a display image when an image is displayed can be increased due to the color purity of the dye itself and the vividness of the hue. . As such dyes, xanthene dyes, dipyrromethene dyes, quinophthalone dyes, triarylmethane dyes, quinoneimine dyes, and the like are known (see, for example, Patent Documents 3 to 7).
In recent years, there has been a demand for further thinning of color filters, and in order to obtain a color filter having spectral characteristics equivalent to those of conventional ones even if the thickness is reduced, it has been studied to increase the relative amount of colorant in the pixel. Yes.

JP-A-2-144502 JP-A-3-53201 JP 2010-032999 A JP 2014-066695 A JP 2011-122125 A International Publication No. 2011/152379 Pamphlet JP 2012-155183 A

However, dyes usually used in coloring compositions for forming color filters are remarkably lacking in heat resistance due to their fragile pigment skeleton, so there are many problems as coloring compositions for color filters, and it is difficult to put them into practical use. . Moreover, many dyes generally have poor solubility in organic solvents, and there are cases where a coating film foreign matter is formed on the formed pixels. In addition, increasing the relative amount of colorants such as dyes in order to meet the recent demand for thin films reduces the relative amount of components that contribute to curability in the colored composition, so that it adheres to the substrate. Sexuality may be insufficient.
Therefore, the subject of this invention is providing the coloring composition which can form the colored cured film which is excellent in heat resistance and board | substrate adhesiveness, and is hard to produce a coating-film foreign material. Furthermore, the subject of this invention is providing the display element and solid-state image sensor which comprise the colored cured film formed using the said coloring composition, and this colored cured film.

  The present inventors have conducted intensive studies in view of such circumstances, and found that the above problems can be solved by using a polymer having a specific structure, and have completed the present invention.

  That is, the present invention is a colored composition comprising (A) a colorant, (B) resin and (C) a polymerizable compound, wherein (B) resin has the same (b1) cationic site and anionic site. The present invention provides a coloring composition containing a polymer contained in a molecule.

  If the coloring composition of this invention is used, it can be excellent in heat resistance and board | substrate adhesiveness, and can form the colored cured film which is hard to produce a coating-film foreign material. Therefore, the colored composition of the present invention can be used very suitably for the production of solid-state imaging devices such as color liquid crystal display devices, organic EL display devices, display devices such as electronic paper, and CMOS image sensors.

Hereinafter, the present invention will be described in detail.
Coloring composition will be described in detail components of the colored composition of the present invention.

-(A) Colorant-
The (A) colorant in the present invention can be used without any particular limitation, and the color and material can be appropriately selected according to the use such as a color filter. Specific examples of the colorant include pigments and dyes, and these can be used alone or in combination of two or more. Especially this invention is preferable at the point which can form the colored cured film excellent in heat resistance, even when it contains a dye as a coloring agent.

  As the pigment, for example, a compound classified as a pigment in the color index (CI; issued by The Society of Dyers and Colorists), that is, the following color index (CI) number 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. Red pigments such as CI Pigment Red 264;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Green pigments such as CI Pigment Green 59;
C. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment blue 79, C.I. I. Blue pigments such as CI Pigment Blue 80;
C. I. Pigment yellow 83, C.I. I. Pigment yellow 138, 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. Yellow pigments such as CI Pigment Yellow 215;
C. I. Orange pigments such as CI Pigment Orange 38;
C. I. Pigment violet 19, C.I. I. Purple pigment such as CI Pigment Violet 23.

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

  In the present invention, 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. Further, these pigments may be used by modifying the particle surface with a resin, if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. As a resin coating method on the carbon black surface, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed. The organic pigment may be used after the primary particles are refined by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Laid-Open No. 8-179111 can be employed.

  The dye is not particularly limited. For example, a known dye may be used in addition to a compound classified as a dye in the color index (CI; issued by The Society of Dyer's and Colorists). Can do.

Such dyes include, for example, xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, quinophthalone dyes, coumarin dyes, pyrazolone dyes, quinoline dyes, nitro dyes from the structural aspect of chromophores. And dyes, quinoneimine dyes, phthalocyanine dyes, squarylium dyes, and the like.
Also, any of acidic dyes, basic dyes and nonionic dyes can be suitably used. Here, in the present specification, the “acidic dye” means an ionic dye in which the anion part becomes a chromophore, and the ionic dye forming a salt with the anion part is also an acid dye. 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 xanthene dyes 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. Acid Red 388, Synthesis Examples 1 to 3 of JP 2010-32999 A, Xanthene acidity disclosed in JP 2011-138094 A; I. In addition to xanthene basic dyes such as Basic Violet 11, compounds described in paragraph [0010] of JP2013-053292A, and formulas (A1) to (A6) described in Examples of JP2013-100343A ), Paragraphs [0038] to [0043] and paragraphs [0048] to [0050] of JP2012-181505A, paragraphs [0036] to [0038] of JP2013-007032A, etc. Can be used.

  Examples of the triarylmethane dye include C.I. I. Triarylmethane acid dyes such as Acid Blue 9; I. In addition to the triarylmethane basic dyes described in Basic Blue 7, International Publication No. 2010/123071, Pamphlet, JP-A 2011-116803, JP-A 2011-1171995, JP-A 2011-133844, etc. JP 2001-011336 A, JP 2003-246935 A, JP 2008-304766 A, JP 2010-256598 A, JP 2011-007847 A, JP 2011-070172 A, JP 2011. -227408, International Publication No. 2011/152379, International Publication No. 2011-162217, Japanese Unexamined Patent Publication No. 2012-017425, Japanese Unexamined Patent Publication No. 2012-037740, International Publication No. 2012/036085, 2012-073291, International Publication No. 2012/053201, Pamphlet of JP2012-083552, JP2012-088615, JP2012-098522, JP2013-057053, US Patent Application The compounds described in Japanese Patent Publication No. 2013/0141810, International Publication No. 2013/147099, etc. can be used.

  Examples of cyanine dyes include C.I. I. Cyanine acid dyes such as Reactive Yellow 1; 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. In addition to cyanine basic dyes such as Basic Yellow 51, components (A-2) to (A-6) described in Examples of JP2009-235392A, paragraphs of JP2012-212089A [0096] To [0108], compounds described in paragraphs [0054] to [0063] of JP2012-214718, paragraphs [0050] to [0054] of JP2012-214719A, The described compounds and the like can be used.

  Examples of the anthraquinone dye include C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Anthraquinone acid dyes such as Reactive Blue 49; I. Bat Blue 4, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. In addition to anthraquinone nonionic dyes such as Disperse Blue 60, compounds described in paragraph [0049] of JP2013-053292A, paragraphs of JP2000-129150A and JP2008-015530A [ The compounds described in JP-A-2013-210621 and the like can be used.

  Examples of the azo 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. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Moldant Black 7, C.I. I. Azo acid dyes such as Direct Green 28; I. Basic Blue 41, C.I. I. Basic red 18, an azo basic dye described in JP2011-145540A; I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. In addition to Disperse Blue 165, azo nonionic dyes described in JP 2010-170073 A, JP 2010-170074 A, JP 2010-275531 A, and JP 2010-275533 A; JP-A-510398, JP-A-2005-226022, JP-A-2007-212439, JP-A-2010-152160, JP-A-2010-170073, JP-A-2011-148993, JP-A-2011-148994. Pyridone azo dyes described in JP-A No. 2011-148995, JP-A 2012-041461, JP-A 2012-066241, WO 2012/039361, pamphlet 2012-194200; JP 04-249549 Diazo dyes described in JP-A No. 2005-120132, JP-A 2005-298636, JP-A 2007-197538, JP-A 2010-275531, JP-A 2012-141429, etc .; Monoazo dyes described in JP-A-2004-325864, JP-A-2010-275533, etc .; JP-A-2005-274788, JP-A-2005-290351, 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 .; for example, JP-A-2007-293127 Paragraphs [0058] to [0061], JP-A-2 In addition to the azomethine dyes described in paragraph [0014] of JP-A No. 11-219655, JP-A-2013-145258, etc., JP-A 2010-150416, JP-A 2010-152159, JP-A 2010-170074. JP-A 2011-016974, JP-A 2011-074270, JP-A 2011-145540, US Patent Application Publication No. 2013/0164681, and the like can be used.

  Examples of the dipyrromethene dye include dipyrromethene compounds containing a polymerizable group described in JP2011-180306A, in addition to the compounds described in JP2008-292970A.

  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 or a compound represented by the formula (1) described in JP 2013-209614 A can be used.

  Examples of the coumarin dye include a compound described in Example 4 of JP-A-4-179955, a compound represented by the formula (1) described in JP2013-151668A, and JP2013-231165A. And a compound represented by the formula (1) described in JP 2014-044419 A can be used.

  As the pyrazolone dye, for example, a compound represented by the formula (1) described in JP-A-2006-016564 and a compound represented by the formula (1) described in JP-A-2006-0663171 are used. Can do.

  Examples of quinoline dyes include C.I. I. Quinoline acid dyes such as Acid Yellow 3; I. Solvent Yellow 33, C.I. I. There may be mentioned quinoline nonionic dyes such as Disperse Yellow 64.

  Examples of the nitro dye include C.I. I. Acid Yellow 1, C.I. I. Nitro acid dyes such as Acid Orange 3; I. Non-ionic dyes such as Disperse Yellow 42 can be mentioned.

  Examples of quinoneimine dyes include C.I. I. Basic Blue 3, C.I. I. A quinoneimine basic dye such as Basic Blue 9 can be mentioned.

  Examples of the phthalocyanine dye include C.I. I. Phthalocyanine nonionic dyes such as Pad Blue 5; in addition to the compounds described in JP-A Nos. 2004-233504 and 2006-047497, paragraphs [0147] to [0155] of JP-A-2007-094181 Can be used.

  As a squarylium dye, the compound described in Unexamined-Japanese-Patent No. 2012-013945, Unexamined-Japanese-Patent No. 2013-076926, international publication 2013/094827 pamphlet etc. can be used, for example.

  In addition, various basic dyes described in JP-T-2007-503477; I. It is also possible to use methine nonionic dyes such as Solvent Yellow 179 and Disperse Yellow 201, and various nonionic dyes described in claim 3 or claim 4 of JP2010-168531A.

  In the present invention, these dyes can be appropriately selected and used. Of these, xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are preferable from the viewpoint of heat resistance.

  In the present invention, a known dispersion aid can be further contained. Known dispersion aids include pigment derivatives, and specific examples include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

  (A) The content ratio of the colorant is usually 5 to 70% by mass in the solid content of the coloring composition from the viewpoint of forming a pixel having excellent luminance and heat resistance, or a black matrix and black spacer having excellent light shielding properties. Preferably, it is 10-60 mass%. Here, solid content is components other than the solvent mentioned later.

-(B) Resin-
The colored composition of the present invention needs to contain (b1) a specific polymer, but in addition to this, it may further contain a binder resin or a dispersant different from (b1). Hereinafter, (b1) the specific polymer will be described first.

  (B1) The specific polymer has a cationic site and an anionic site in the same molecule, in other words, has a zwitterionic structure. In the present specification, the specific polymer (b1) is, for example, a salt of a polymer having only an anionic site and no anionic site, such as sodium polystyrene sulfonate, and a counter cation, or having an anionic site. First, a salt of a polymer having only a cationic site and a counter anion is not included. (B1) The specific polymer preferably has a cationic site and an anionic site at positions not adjacent to each other in the same molecule, and a positively charged atom in the cationic site has a dissociable hydrogen atom. Preferably they are not bonded.

  The specific polymer (b1) in the present invention is an ethylenically unsaturated monomer having a cationic site and an anionic site (hereinafter referred to as “unsaturated monomer (b1-1)” from the viewpoint of availability of raw materials. The polymer of a monomer containing ")" is preferable, and is selected from a polymer having a repeating unit represented by the following formula (1) and a polymer having a repeating unit represented by the following formula (2). At least one selected from the above is preferred.

[In Formula (1),
R ¹¹ represents a hydrogen atom or a methyl group,
R ¹² and R ¹³ each independently represent a divalent organic group,
^{(C 1) + is,} -N ^{+ R} 14 ^{R 15} - or ^-P + ^R 16 ^{R 17} - indicates,
R ^{14 to} R ¹⁷ each independently represent a monovalent organic group,
(A ¹ ) ⁻ represents CO ₂ ⁻ , SO ₃ ^— or PO ₄ ^— . ]

[In Formula (2),
R ²¹ represents a hydrogen atom or a methyl group,
R ²² and R ²³ each independently represent a divalent organic group,
^{(A 2)} - ^{is, -OP (= O) (-} O -) O -, - SO 2 N - SO 2 - or ^{-C (= O) N - SO} 2 - indicates,
(C ² ) ⁺ represents N ⁺ R ²⁴ R ²⁵ R ²⁶ or P ⁺ R ²⁷ R ²⁸ R ²⁹ ,
R ²⁴ to R ²⁹ are independently of each other, a monovalent organic group. ]

The divalent organic group in R ¹² , R ¹³ , R ²² and R ²³ is a combination of a divalent hydrocarbon group, a divalent hydrocarbon group and a linking group containing an atom other than a carbon atom and a hydrogen atom. Or a group in which part of the hydrogen atoms of these groups is substituted with a halo group. Examples of such an organic group include an alkanediyl group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, an arylene alkanediyl group having 7 to 20 carbon atoms, or an alkanediyl group having 1 to 10 carbon atoms. At least one selected from a group and an arylene group having 6 to 20 carbon atoms, -O-, -S-, -COO-, -CONR ^b- (R ^b is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. And a group formed by combining at least one selected from —SO ₂ — and the like.

The alkanediyl group may be linear or branched. For example, a methylene group, ethylene group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane- 1,3-diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4-diyl Group, pentane-1,5-diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, etc. Mention may be made of 1 to 10 alkanediyl groups.
Examples of the arylene group include arylene groups having 6 to 10 carbon atoms such as a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group.
An arylene alkanediyl group is a divalent group formed by combining an arylene group and an alkanediyl group. For example, a phenylenemethylene group, a phenylenedimethylene group, a phenylenetrimethylene group, a phenylenetetramethylene group, or a phenylenepentamethylene group. And a phenylene C _1-6 alkanediyl group such as a phenylenehexamethylene group.

And at least one selected from an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms, -O-, -S-, -COO-, -CONR ^b- (R ^b is a hydrogen atom Or an alkyl group having 1 to 8 carbon atoms) and a group formed by combining at least one selected from —SO ₂ — and an alkanediyl group having 1 to 10 carbon atoms and an arylene having 6 to 20 carbon atoms. A group formed by combining at least one selected from a group and at least one selected from —O—, —COO—, and —SO ₂ — is preferable, and is an alkanediyl group having 1 to 10 carbon atoms and 6 to 6 carbon atoms. A group formed by combining at least one selected from 20 arylene groups and at least one selected from —O— and —SO ₂ — is more preferable. Specific examples of the alkyl group having 1 to 8 carbon atoms according to R ^b 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, and a tert-butyl group. Hexyl group, heptyl group, octyl group and the like.

Among them, as the divalent organic group in R ¹² and R ²² , an alkanediyl group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an alkanediyl group having 1 to 10 carbon atoms and 6 carbon atoms. A group formed by combining at least one selected from ˜20 arylene groups and at least one selected from —O—, —S—, —COO—, —CONR ^b —, and —SO ₂ —; At least one selected from an arylene group having 6 to 10 carbon atoms, or an alkanediyl group having 1 to 8 carbon atoms and an arylene group having 6 to 10 carbon atoms, and —O—, —COO—, —CONR ^b — and —SO _A group formed by combining at least one selected from _2- is more preferable. In addition, at least one selected from an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms, and —O—, —S—, —COO—, —CONR ^b —, and —SO ₂ —. In the group formed by combining at least one selected, it is preferable that the alkanediyl group having 1 to 10 carbon atoms is bonded to (C ¹ ) ⁺ or (A ² ) ⁻ .
Moreover, as a bivalent organic group in R <^13> and R < ²³ >, a C1-C10 alkanediyl group, a C6-C20 arylene group, or a C7-C20 arylene alkanediyl group is preferable, A C1-C5 alkanediyl group is more preferable, and a methylene group, an ethylene group, a propane-1,3-diyl group, and a pentane-1,5-diyl group are still more preferable.

(C ¹ ) ⁺ in formula (1) is a divalent linking group represented by —N ⁺ R ¹⁴ R ¹⁵ — or —P ⁺ R ¹⁶ R ¹⁷ —, and (C ² in formula (2) ) ⁺ Is a monovalent functional group represented by N ⁺ R ²⁴ R ²⁵ R ²⁶ or P ⁺ R ²⁷ R ²⁸ R ²⁹ . Here, monovalent organic groups according to R ^{14 to} R ¹⁷ and R ^{24 to} R ²⁹ include monovalent hydrocarbon groups, and such monovalent hydrocarbon groups include monovalent aliphatic groups. Any of a hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group may be used. The monovalent aliphatic hydrocarbon group may be either linear or branched, and the monovalent aliphatic hydrocarbon group and the monovalent alicyclic hydrocarbon group are saturated carbon atoms. It may be a hydrogen group or an unsaturated hydrocarbon group. The position of the unsaturated bond of the unsaturated hydrocarbon group may be either in the molecular chain or at the end of the molecular chain, and can be at any position. Here, in the present specification, the “alicyclic hydrocarbon group” is a concept excluding an aliphatic hydrocarbon group having no cyclic structure. In addition, in this specification, “alicyclic hydrocarbon group” and “aromatic hydrocarbon group” are not only a group consisting of only a ring structure, but also a divalent aliphatic hydrocarbon group substituted on the ring structure. In other words, the structure includes at least an alicyclic hydrocarbon or an aromatic hydrocarbon. Further, the monovalent hydrocarbon group may have a substituent within a range not departing from the gist of the present invention. The position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different. Examples of the substituent include a cyano group, a formyl group, a nitro group, a trialkylsilyl group, an alkoxy group, an aryloxy group, and a heterocyclic group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the monovalent aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. Carbon number of an aliphatic hydrocarbon group becomes like this. Preferably it is 1-30, More preferably, it is 1-20, More preferably, it is 1-12. Specific examples of the alkyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, and nonyl. Group, decyl group, undecyl group, 1-methyldecyl group, dodecyl group, 1-methylundecyl group, 1-ethyldecyl group, tridecyl group, tetradecyl group, tert-dodecyl group, pentadecyl group, 1-heptyloctyl group, hexadecyl group And octadecyl group. Specific examples of the alkenyl group include, for example, ethenyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1,3-butadienyl group, 1-pentenyl group, 2-pentenyl group, A 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. Specific examples of the alkynyl group include, for example, ethynyl group, 1-propynyl group, 1-butynyl group, 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 can be mentioned.

Examples of the monovalent alicyclic hydrocarbon group include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged ring hydrocarbon group, a spiro hydrocarbon group, and a cyclic terpene hydrocarbon group. Can do. Carbon number of an aliphatic hydrocarbon group becomes like this. Preferably it is 3-30, More preferably, it is 3-20, More preferably, it is 3-12. Specific examples of the cycloalkyl group include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a t-butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. Specific examples of the cycloalkenyl group include Examples thereof include 1-cyclohexenyl group. Specific examples of the condensed polycyclic hydrocarbon group include tricyclodecanyl group, decahydro-2-naphthyl group, adamantyl group and the like. Specific examples of the bridged cyclic hydrocarbon group include, for example, Examples include tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, pentacyclopentadecanyl group, isobonyl group, dicyclopentenyl group, tricyclopentenyl group and the like. Furthermore, examples of the spiro hydrocarbon group include a monovalent group obtained by removing one hydrogen atom from spiro [3,4] heptane, spiro [3,4] octane, and the cyclic terpene hydrocarbon group. Examples thereof include a monovalent group obtained by removing one hydrogen atom from p-menthane, tsujang, curan and the like.

  Examples of the monovalent aromatic hydrocarbon group include an aryl group and an aralkyl group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenylene group, an azulenyl group, and a 9-fluorenyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, A trityl group etc. are mentioned.

(C ¹ ) ⁺ in formula (1) is preferably -N ⁺ R ¹⁴ R ^15- from the viewpoint of availability of raw materials and heat resistance, and (C ² ) ⁺ in formula (2). Is preferably N ⁺ R ²⁴ R ²⁵ R ²⁶ . In this case, R ^{14 to} R ¹⁵ and R ^{24 to} R ²⁶ are preferably a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group. Although these preferable aspects are as above-mentioned, it is more preferable that they are a C1-C8 alkyl group and a C6-C10 aryl group, and a C1-C4 alkyl group and a phenyl group are especially preferable. .

(A ¹ ) ⁻ in the formula (1) represents CO ₂ ⁻ , SO ₃ ^— or PO ₄ ^— , and CO ₂ ⁻ and SO ₃ ^— are preferable from the viewpoint of availability of raw materials and heat resistance. ₃ ^- it is more preferable.
(A ² ) ⁻ in the formula (2) is represented by —OP (═O) (— O ⁻ ) O—, —SO ₂ N ^— SO ₂ — or —C (═O) N ^— SO ₂ —. it is a divalent linking group, from the viewpoint of availability and heat resistance of the material, -OP (= O) (- O -) O- or _-SO 2 ^N - SO ₂ - are preferred, -OP (= O) (— O ⁻ ) O— is more preferable.

  (B1) When the specific polymer is a polymer having a repeating unit represented by the formula (1) or a polymer having a repeating unit represented by the following formula (2), the polymer is further another repeating unit. You may have. In this case, the content ratio of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) in the polymer is preferably 3 to 90% by mass, more preferably 5 to 60% by mass, 10-40 mass% is still more preferable.

As a monomer which gives the repeating unit represented by the formula (1), N- (meth) acryloyloxyethyl N, N-dimethylammonium-α-N-ethylcarboxylate, [2- (methacryloyloxy) ethyl] Examples include dimethyl- (3-sulfopropyl) ammonium hydroxide. In addition, a monomer synthesized according to the method described in JP-A 09-095474, or a reaction product of a phosphine having a polymerizable unsaturated group and a sultone can be used.
Examples of the monomer that gives the repeating unit represented by the formula (2) include 2- (meth) acryloyloxyethyl phosphorylcholine.

  As a monomer which gives the other repeating unit which the polymer which has a repeating unit represented by Formula (1) and the polymer which has a repeating unit represented by following formula (2) may contain, it mentions later. (B2) The unsaturated monomer (b2-1) and unsaturated monomer (b2-2) illustrated in the binder resin can be mentioned. Lipidure (registered trademark, manufactured by NOF Corporation) and the like can also be used as the polymer having the repeating unit represented by the formula (2).

(B1) A known method can be employed for the synthesis reaction of the specific polymer, and examples thereof include anionic polymerization, living anion polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. it can.
(B1) The molecular weight of the specific polymer is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, as the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC).
Moreover, (b1) Ratio (Mw / Mn) of the weight average molecular weight (Mw) and number average molecular weight (Mn) of a specific polymer becomes like this. Preferably it is 1.0-5.0, More preferably, it is 1.0-3. .0. Here, Mw and Mn are polystyrene-reduced number average molecular weights measured by GPC (elution solvent: tetrahydrofuran).

Next, the binder resin and dispersant that may be contained in the colored composition of the present invention will be described.
The colored composition of the present invention preferably contains (b2) a binder resin (excluding the (b1) specific polymer) together with (b1) the specific polymer from the viewpoints of storage stability and developability. (B2) The binder resin is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). And a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as “unsaturated monomer (b2-2)”). Can be mentioned. Binder resin can be used 1 type or in mixture of 2 or more types.

Examples of the unsaturated monomer (b2-1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono ( And (meth) acrylate, p-vinylbenzoic acid, and the like.
An unsaturated monomer (b2-1) can be used 1 type or in mixture of 2 or more types.

Moreover, as an unsaturated monomer (b2-2), for example,
N-substituted maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 -10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) ) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
An unsaturated monomer (b2-2) can be used 1 type or in mixture of 2 or more types.

  In the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2), the copolymerization ratio of the unsaturated monomer (b2-1) in the copolymer is preferably Is 5-50 mass%, More preferably, it is 10-40 mass%. By copolymerizing the unsaturated monomer (b2-1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

  Specific examples of the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) include, for example, JP-A-7-140654 and JP-A-8-259876. It is disclosed in Kaihei 10-31308, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin. In the colored composition of the present invention, (b2) a highly sensitive colored composition is obtained by using a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain as the binder resin. It is preferable in that it can be improved and the curability of the coating film can be increased.

  (B2) The binder resin can be produced by a known method, and is disclosed, for example, in JP 2003-222717 A, JP 2006-259680 A, and International Publication No. 2007/029871. The structure, Mw, and Mw / Mn can be controlled by the method.

The (b2) binder resin in the present invention has an Mw measured by GPC of usually 1,000 to 100,000, preferably 3,000 to 50,000. By setting it as such an aspect, while heat resistance is improved further, foreign material generation | occurrence | production can be suppressed effectively.
Moreover, Mw / Mn of (b2) binder resin in this invention becomes like this. Preferably it is 1.0-5.0, More preferably, it is 1.0-3.0.

  When the colored composition of the present invention contains a pigment as the colorant (A), (B) a dispersant (excluding the specific polymer (b1) above) is included as a resin. To preferred. (B3) Examples of the dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkyl phenyl ether dispersant, a polyethylene glycol diester dispersant, and a sorbitan fatty acid ester. Examples thereof include system dispersants, polyester dispersants, and acrylic dispersants.

  Such a (b3) dispersant is commercially available. For example, as an acrylic dispersant, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (above, Big Chemie ( BYK)), and the like, Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 Lubrizol Co., Ltd.), polyethylene imine dispersant, Solsperse 24000 (Lubrisol Co., Ltd.), etc., polyester dispersant, Ajispa PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881 (or, Ajinomoto Fine-Techno Co., Ltd.) other such, BYK-LPN21324 the (Chemie (BYK) Co., Ltd.) can be mentioned, respectively.

In the present invention, the content of the (b1) specific polymer is usually 1 to 200 parts by weight, preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the (A) colorant. Part. By setting it as such an aspect, not only the storage stability of a coloring composition improves and the heat resistance of a cured film is improved, but generation | occurrence | production of a foreign material can be suppressed effectively. Moreover, content of (b2) binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts, More preferably, it is 50-200 mass parts. . By setting it as such an aspect, alkali developability, the storage stability of a coloring composition, a pattern shape, and chromaticity characteristic can be improved further, and generation | occurrence | production of a deposit and a coating-film foreign material can be suppressed.
Moreover, content of (b3) dispersing agent is 1-100 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 5-70 mass parts, More preferably, it is 10-50 mass parts.

-(C) Polymerizable compound-
In the present invention, the polymerizable compound refers to 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 (C) is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups. (C) A polymeric compound can be used 1 type or in mixture of 2 or more types.

  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, a polyfunctional (meta) modified with caprolactone. ) Acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting hydroxyl-functional (meth) acrylate and polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group obtained by making a product react can be mentioned.

  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. Mention may be made of aliphatic polyhydroxy compounds having a valence higher than that. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol dihydrate. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. The alkylene oxide-modified polyfunctional (meth) acrylate is at least one selected from bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide. Modified with at least one selected from trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from modified isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide Pen modified with at least one selected from pentaerythritol tri (meth) acrylate, ethylene oxide and propylene oxide. Dipentaerythritol modified with at least one selected from dipentaerythritol penta (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from taerythritol tetra (meth) acrylate, ethylene oxide and propylene oxide Examples include hexa (meth) acrylate.

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

  Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethanes (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N ′ -Tetra (alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Among polyfunctional (meth) acrylates having a carboxyl group, erythritol hexaacrylate is obtained by reacting pentaerythritol triacrylate and succinic anhydride, and reacting dipentaerythritol pentaacrylate and succinic anhydride. A compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and foreign matter is hardly generated.

  The content of the polymerizable compound (C) in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 800 parts by mass, and 100 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. Is more preferable. By setting it as such an aspect, the pixel excellent in heat resistance, or the black matrix and black spacer excellent in light-shielding property can be formed.

-Photopolymerization initiator-
The coloring composition of the present invention can contain a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of the polymerizable compound (C) by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. . A photoinitiator can be used 1 type or in mixture of 2 or more types.

  Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone compound, a polynuclear quinone compound, a diazo compound, an imide sulfonate compound, an onium salt compound, etc. can be mentioned. Among these, at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds is preferable.

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

  Specific examples of acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- And morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′- Bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 Examples include ', 5,5'-tetraphenyl-1,2'-biimidazole.

  In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, the hydrogen donor can be used singly or in combination of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

  Specific examples of the triazine compound include compounds described in paragraphs [0063] to [0065] of JP-B-57-6096 and JP-A-2003-238898.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -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. As commercial products of O-acyloxime compounds, NIC-730, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), OXE-03, OXE-04 (above, manufactured by BASF Corporation), etc. are used. You can also

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

  In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) polymeric compounds, and, as for content of a photoinitiator, 1-100 mass parts is still more preferable. By setting it as such an aspect, not only suppression of the generation | occurrence | production of a foreign material but sclerosis | hardenability and a film characteristic can be made favorable.

-Solvent-
The coloring composition of the present invention contains the above components (A) to (C) and other components optionally added, but is usually prepared as a liquid composition by blending an organic solvent. .
As an organic solvent, as long as (A)-(C) component and other components which comprise a coloring composition are disperse | distributed or melt | dissolved, and it does not react with these components and has moderate volatility, it is suitably You can choose to use. A solvent can be used 1 type or in mixture of 2 or more types.

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 acetates such as 3-methyl-3-methoxybutyl acetate;
Cyclic ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

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

  Among these solvents, at least one selected from (poly) alkylene glycol monoalkyl ether and (poly) alkylene glycol monoalkyl ether acetate is preferable from the viewpoints of solubility, pigment dispersibility, coatability and the like.

  Although content of a solvent is not specifically limited, The quantity from which the total density | concentration of each component except the solvent of the coloring composition becomes 5-50 mass% is preferable, and the quantity used as 10-40 mass% More preferred. By setting it as such an aspect, the coloring agent dispersion liquid with favorable dispersibility and stability and the coloring composition with favorable applicability | paintability can be obtained.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicone 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-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: 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-butane Such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. Examples include developability improvers.

Preparation Method of Colored Composition The colored composition of the present invention can be prepared by an appropriate method. Examples of the preparation method include (A) to (C), a solvent, and other optional additives. It can prepare by mixing with the component of. (A) When the colorant contains a pigment, the pigment is pulverized in a solvent in the presence of (b3) a dispersant, optionally with (b2) a part of the binder resin, for example, using a bead mill, a roll mill or the like. Mix and disperse to obtain a pigment dispersion, and then add (b1) a specific polymer and (C) a polymerizable compound, and (b2) a binder resin and a photopolymerization initiator, if necessary. The method of preparing by adding and mixing the solvent and other components.

Colored cured film and method for forming the same A colored cured film used for a color filter constituting a display element or a solid-state imaging element and a method for forming the same will be described below.
As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, a blue liquid composition of the radiation-sensitive colored composition of the present invention is applied on the substrate, and then pre-baked to evaporate the solvent to form a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which blue pixel patterns (colored cured films) are arranged in a predetermined arrangement.

  Subsequently, using each radiation sensitive coloring composition of green or red, application of each radiation sensitive coloring composition, pre-baking, exposure, development, and post-baking are performed in the same manner as described above to obtain a green pixel array and red color. Are sequentially formed on the same substrate. Thereby, a color filter in which a pixel array of the three primary colors of blue, green and red is arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithographic method. However, it is a radiation sensitive material in which a black colorant is dispersed. A colored composition can be used in the same manner as in the case of forming the pixel.

  Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  When applying the radiation-sensitive coloring composition to the substrate, an appropriate coating method such as spraying, roll coating, spin coating (spin coating), slit die coating (slit coating), bar coating, etc. In particular, it is preferable to employ a spin coating method or a slit die coating method.

  Prebaking is usually about 1 to 10 minutes at 70 to 110 ° C.

  The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 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, and a low pressure. Examples thereof include a lamp light source such as a mercury lamp, and a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The wavelength is preferably radiation in the range of 190 to 450 nm.

Exposure of the radiation is generally preferred 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, and 1,8-diazabicyclo- [5.4.0] -7-undecene. An aqueous solution of 1,5-diazabicyclo- [4.3.0] -5-nonene is preferable.

For example, 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. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

  Further, as a second method for producing a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723 and JP-A-2000-310706 can be employed. . In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, a liquid composition of a blue thermosetting coloring composition is discharged into the formed partition wall by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, the coating film is exposed as necessary, and then cured by post-baking to form a blue pixel pattern.

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

In addition, since the partition plays not only a light shielding function but also a function for preventing the color mixing of the thermosetting coloring compositions discharged in the respective sections, it is compared with the black matrix used in the first method described above. The film thickness is thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

  A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a radiation-sensitive colored composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for forming such a black spacer.

  The colored composition of the present invention can be suitably used in forming any colored cured film such as each color pixel, black matrix, and black spacer used in a color filter. Since the color filter having the colored cured film of the present invention thus formed has extremely high luminance and color purity, it can be used in color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like. Very useful. In addition, the display element mentioned later should just have at least 1 or more of the colored cured film formed using the coloring composition of this invention.

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, and electronic paper.
The color liquid crystal display element provided with the colored cured film of the present invention may be a transmissive type or a reflective type, and can take an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. Can be taken. Further, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (indium oxide doped with tin) electrode or an IZO (mixture of acid value indium and zinc oxide) electrode It is also possible to adopt a structure in which the substrate on which the substrate is formed faces the liquid crystal layer. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained. When the latter structure is adopted, the black matrix or the black spacer may be formed on either the substrate side on which the color filter is formed, or on the substrate side on which the ITO electrode or IZO electrode is formed.

  The color liquid crystal display element including the colored cured film of the present invention can include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence A white LED that obtains white light by color mixing by combining the body, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

  The color liquid crystal display element having the colored cured film of the present invention includes TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Plane Switching) type, VA (Vertical Alignment) type, OCB (Optical). An appropriate liquid crystal mode such as a Compensated Birefringence type is applicable.

  The organic EL display element provided with the colored cured film of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242. Moreover, the electronic paper provided with the cured film of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-2007-41169.

Solid-state image sensor The solid-state image sensor of the present invention comprises the colored cured film of the present invention. In addition, the solid-state imaging device of the present invention can take an appropriate structure. For example, as one embodiment, by using the colored composition of the present invention and forming a colored pixel (colored cured film) on a semiconductor substrate such as a CMOS substrate by the same operation as described above, color separation is achieved. And a solid-state imaging device having excellent color reproducibility.

  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.

<Resin synthesis>
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate 23 parts by mass, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) The solution was added dropwise over a period of time and polymerized for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a resin solution (B-1) (solid content concentration: 33% by mass). The obtained resin had Mw of 12,200 and Mn of 6,500. This resin corresponds to (b2) a binder resin.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 35 parts by mass of a compound represented by the following formula (Bet-1), 13 parts by mass of methacrylic acid, 6.5 parts by mass of styrene, benzyl Methacrylate 3.2 parts by weight, 2-hydroxyethyl methacrylate 9.8 parts by weight, 2-ethylhexyl methacrylate 15 parts by weight, N-phenylmaleimide 7.8 parts by weight, succinic acid mono (2-acryloyloxyethyl) 9.7 A mixed solution of 5 parts by mass and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a resin solution (B-2) (solid content concentration: 33% by mass). This resin corresponds to (b1) the specific polymer.

Synthesis example 3
In Synthesis Example 2, a resin solution (B-3) was prepared in the same manner as in Synthesis Example 2 except that a compound represented by the following formula (Bet-2) was used instead of the compound represented by the formula (Bet-1). ) (Solid content concentration 33% by mass). This resin corresponds to (b1) the specific polymer. The compound represented by the formula (Bet-2) was synthesized by the method described later.

Synthesis example 4
In Synthesis Example 2, a resin solution (B-4) was prepared in the same manner as in Synthesis Example 2 except that a compound represented by the following formula (Bet-3) was used instead of the compound represented by the formula (Bet-1). ) (Solid content concentration 33% by mass). This resin corresponds to (b1) the specific polymer.

Synthesis example 5
In Synthesis Example 2, a resin solution (B-5) was prepared in the same manner as in Synthesis Example 2 except that a compound represented by the following formula (Bet-4) was used instead of the compound represented by the formula (Bet-1). ) (Solid content concentration 33% by mass). This resin corresponds to (b1) the specific polymer.

Synthesis Example 6
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 80 parts by mass of a compound represented by the following formula (Bet-1), 4 parts by mass of methacrylic acid, 2 parts by mass of styrene, benzyl methacrylate 1 Parts by weight, 3 parts by weight of 2-hydroxyethyl methacrylate, 4.6 parts by weight of 2-ethylhexyl methacrylate, 2.4 parts by weight of N-phenylmaleimide, 3 parts by weight of succinic acid mono (2-acryloyloxyethyl) and 2,2 A mixed solution of 6 parts by mass of '-azobis (2,4-dimethylvaleronitrile) was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a resin solution (B-6) (solid content concentration: 33% by mass). This resin corresponds to (b1) the specific polymer.

Synthesis example 7
In Synthesis Example 2, a resin solution (B-7) was prepared in the same manner as in Synthesis Example 2 except that a compound represented by the following formula (Anm-1) was used instead of the compound represented by the formula (Bet-1). ) (Solid content concentration 33% by mass). This resin corresponds to (b2) a binder resin.

Synthesis Example 8
In Synthesis Example 2, a resin solution (B-8) was prepared in the same manner as in Synthesis Example 2 except that a compound represented by the following formula (Slf-1) was used instead of the compound represented by the formula (Bet-1). ) (Solid content concentration 33% by mass). This resin corresponds to (b2) a binder resin.

Synthesis Example 9
2.88 g (10 mmol) of p-styryldiphenylphosphine and 1.22 g (10 mmol) of 1,3-propane sultone were heated to reflux in 30 mL of toluene for 24 hours. The precipitate was washed with a small amount of toluene and dried under reduced pressure to obtain 2.5 g (6.2 mmol) of a compound represented by the following formula (Bet-2).

<Preparation of colorant solution>
Preparation Example 1
A colorant solution (1) was prepared by mixing 10 parts by mass of the compound (A-1) represented by the following formula and 90 parts by mass of ethyl lactate.

Preparation Examples 2-14
In Preparation Example 1, the colorant solutions (2) to (14) were prepared in the same manner as Preparation Example 1 except that the compounds (A-2) to (A-14) were used instead of the compound (A-1). Prepared. Compounds (A-2) to (A-14) are as described below.

A-1: Xanthene compound A-2: synthesized in accordance with Synthesis Example 1 of JP2013-190767A, Xanthene compound A-3: synthesized in accordance with Synthesis Example 3 of JP2013-190776 A synthesis example of JP2013-178478A Xanthene compound A-4: synthesized according to Synthesis Example 1 of JP2014-219663Xanthene compound A-5: cyanine compound described in Chemical Formula 27 of JP2015-049482 (C1-1) 1)
A-6: Triarylmethane compound B described in Chemical formula 20 of International Publication No. 2012/165537 pamphlet
A-7: C.I. I. Solvent Blue 45 (anthraquinone compound)
A-8: C.I. I. Solvent Blue 70 (phthalocyanine compound)
A-9: An azo compound (P1-1) described in Chemical Formula 8 of JP-A-2015-044982
A-10: C.I. I. Solvent Yellow 114 (quinophthalone compound)
A-11: Coumarin compound A-12 described in Example 4 of JP-A-4-179955: Illustrative compound III-1 (dipyrromethene compound) described in Chemical Formula 54 of Japanese Patent No. 5085256
A-13: Compound III-7 (squarylium compound) described in Chemical formula 16 of JP-A-2006-241429
A-14: A compound represented by the formula (2b) described in Dye Synthesis Example 2 of JP 2010-211198 A (a salt-forming compound of a cationic xanthene chromophore and an anionic organometallic complex)

<Preparation of pigment dispersion>
Preparation Example 15
As a coloring agent, C.I. I. Pigment Blue 15: 6 (15 parts by mass), (b3) BYK-LPN21116 (manufactured by BYK Corporation) 12.5 parts by mass (solid content concentration 40% by mass) as a dispersant, propylene glycol monomethyl ether acetate 72. Using 5 parts by mass, a pigment dispersion (a-1) was prepared by processing with a bead mill.

<Preparation and evaluation of coloring composition>
Example 1
(A) 21.3 parts by mass of the pigment dispersion (a-1) and 8.0 parts by mass of the colorant solution (1) as the colorant, and 2.5 parts by mass of the resin solution (B-2) as the resin (B) M-402 (dipentaerythritol hexaacrylate) manufactured by Toagosei Co., Ltd. as a polymerizable compound (solid content concentration 33% by mass) and resin solution (B-1) 10.0 parts by mass (solid content concentration 33% by mass) And dipentaerythritol pentaacrylate) 8.2 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Ciba Specialty Chemicals) as a photopolymerization initiator Company name, product name IRGACURE 369) 0.8 parts by mass and NCI-930 (manufactured by ADEKA) 0.1 part by mass, as a fluorosurfactant, MegaFac F-554 ( IC Co., Ltd.) 0.02 parts by weight, and using propylene glycol monomethyl ether acetate as a solvent, a solid content concentration of 20 mass% of the coloring composition (CR1) was prepared.

Evaluation of heat resistance The coloring composition (CR1) was applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed using a spin coater, and then 2 on a hot plate at 90 ° C. Pre-baking was performed for a minute to form a coating film having a thickness of 2.5 μm. Subsequently, after cooling this board | substrate to room temperature, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed to each coating film with the exposure amount of 400 J / m < ² > through the photomask using the high pressure mercury lamp. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 200 ° C. for 30 minutes to form a dot pattern on the substrate.
About the obtained dot pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), a C light source, a chromaticity coordinate value (x, y) and a stimulus value (Y) in the CIE color system with a 2-degree field of view. Was measured.
Next, after the substrate was additionally baked at 230 ° C. for 90 minutes, the chromaticity coordinate values (x, y) and the stimulus value (Y) were measured, and the color change before and after the additional baking, that is, ΔE ^* _ab was evaluated. . As a result, when the value of ΔE ^* _ab is less than 1.5, “「 ”, when it is 1.5 or more and less than 3.0,“ ◯ ”, when it is 3.0 or more and less than 5.0,“ Δ ”, The case of 5.0 or more was evaluated as “x”. The evaluation results are shown in Table 1. It can be said that the smaller the ΔE ^* _ab value, the better the heat resistance.

Evaluation of substrate adhesion The colored composition (CR1) was applied onto a glass substrate using a spin coater, air-dried, and then a 2.5 μm-thick coating film was formed without pre-baking. Next, after cooling the substrate to room temperature, a high-pressure mercury lamp is applied to the coating film on the substrate through a photomask having dot patterns having different sizes in 5 μm increments from 5 μm to 50 μm through 365 nm, 405 nm, and 436 nm. The radiation containing each wavelength of was exposed at an illuminance of 17 mW and an exposure amount of 600 J / m ² . Then, shower development was performed by discharging the developing solution which consists of 0.04% potassium hydroxide aqueous solution of 23 degreeC with respect to the coating film on a board | substrate with the developing pressure of 1 kgf / cm < ² > (nozzle diameter 1mm). Thereafter, these substrates were washed with ultrapure water and air-dried.
This substrate was observed with an optical microscope. Table 1 shows the size (μm) of the minimum dot pattern resolved without peeling from the substrate. It can be said that the smaller the size, the better the adhesion.

Evaluation of coating film foreign matter After the colored composition (CR1) was applied on a glass substrate using a spin coater, it was pre-baked on a hot plate at 80 ° C. for 10 minutes to form a coating film.
Next, after cooling the substrate to room temperature, using a high-pressure mercury lamp, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was applied to each coating film at a dose of 2,000 J / m ² without using a photomask. Exposed. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230 ° C. for 30 minutes to form a cured film for evaluation.
The cured film for evaluation was observed at a magnification of 50 using an optical microscope, and the number of foreign substances that could be confirmed in the field of view was counted. This operation was performed at arbitrary five locations on the cured film for evaluation, and the following criteria were evaluated from the total of confirmed foreign substances. The results are shown in Table 1.

○: The total number of foreign matters is less than 5 Δ: The total number of foreign matters is 5 or more and less than 50 ×: The total number of foreign matters is 50 or more

Examples 2-5
In Example 1, colored compositions (CR2) to (CR18) were prepared in the same manner as in Example 1 except that the types of the resin solution and the colorant solution were changed as shown in Table 1. Subsequently, evaluation was performed in the same manner as in Example 1 except that the colored compositions (CR2) to (CR18) were used in place of the colored composition (CR1). The results are shown in Table 1.

Comparative Examples 1 to 3 In Example 1, except that the resin solution (B-1), (B-7) or (B-8) was used instead of the resin solution (B-2), the same as in Example 1. Thus, colored compositions (CR19), (CR20), and (CR21) were prepared. Next, evaluation was performed in the same manner as in Example 1 except that the colored compositions (CR19), (CR20), and (CR21) were used instead of the colored composition (CR1). The results are shown in Table 1.

Comparative Example 4 (A) 21.3 parts by mass of the pigment dispersion (a-1) as the colorant and 8.0 parts by mass of the colorant solution (1), (B) 10.0 resin resin (B-1) as the resin Part by mass (solid content concentration: 33% by mass), (C) 8.2 parts by mass of M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Toagosei Co., Ltd. as a polymerizable compound, initiation of photopolymerization 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, trade name IRGACURE 369) as an agent and NCI-930 (stock) 0.1 part by mass of ADEKA (manufactured by ADEKA), 0.02 part by mass of Megafac F-554 (manufactured by DIC Corporation) as a fluorosurfactant, the above formula (Bet- A colored composition (CR22) having a solid content concentration of 20% by mass was prepared using 0.825 parts by mass of the compound represented by 1) and propylene glycol monomethyl ether acetate as a solvent.
Subsequently, evaluation was performed in the same manner as in Example 1 except that the colored composition (CR22) was used instead of the colored composition (CR1). The results are shown in Table 1. In Table 1 (B) Resin column, the amount in parentheses is the amount of each resin solution.

Claims (9)

A coloring composition comprising (A) a colorant, (B) a resin and (C) a polymerizable compound,
(B) The colored composition in which the resin contains a polymer having (b1) a cationic site and an anionic site in the same molecule. (B1) A polymer having a cationic site and an anionic site in the same molecule and a polymer having a repeating unit represented by the following formula (1) and a polymer having a repeating unit represented by the following formula (2) The coloring composition of Claim 1 containing at least 1 sort (s) chosen from coalescence.

[In Formula (1),
R ¹¹ represents a hydrogen atom or a methyl group,
R ¹² and R ¹³ each independently represent a divalent organic group,
^{(C 1) + is,} -N ^{+ R} 14 ^{R 15} - or ^-P + ^R 16 ^{R 17} - indicates,
R ^{14 to} R ¹⁷ each independently represent a monovalent organic group,
(A ¹ ) ⁻ represents CO ₂ ⁻ , SO ₃ ^— or PO ₄ ^— . ]

[In Formula (2),
R ²¹ represents a hydrogen atom or a methyl group,
R ²² and R ²³ each independently represent a divalent organic group,
^{(A 2)} - ^{is, -OP (= O) (-} O -) O -, - SO 2 N - SO 2 - or ^{-C (= O) N - SO} 2 - indicates,
(C ² ) ⁺ represents N ⁺ R ²⁴ R ²⁵ R ²⁶ or P ⁺ R ²⁷ R ²⁸ R ²⁹ ,
R ²⁴ to R ²⁹ are independently of each other, a monovalent organic group. ]   (B1) The colored composition according to claim 2, wherein the content ratio of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) in the polymer is 3 to 90% by mass.   (A) The coloring composition of any one of Claims 1-3 in which a coloring agent contains dye.   The coloring composition according to claim 4, wherein the dye is at least one selected from the group consisting of a xanthene dye, a triarylmethane dye, a cyanine dye, an anthraquinone dye, a dipyrromethene dye, and a phthalocyanine dye.   The colored cured film formed using the coloring composition of any one of Claims 1-5.   A display element comprising the colored cured film according to claim 6.   A solid-state imaging device comprising the colored cured film according to claim 6. The polymer which has a repeating unit represented by following formula (1).

[In Formula (1),
R ¹¹ represents a hydrogen atom or a methyl group,
R ¹² and R ¹³ each independently represent a divalent organic group,
^{(C 1) + is,} -N ^{+ R} 14 ^{R 15} - or ^-P + ^R 16 ^{R 17} - indicates,
R ^{14 to} R ¹⁷ each independently represent a monovalent organic group,
(A ¹ ) ⁻ represents CO ₂ ⁻ , SO ₃ ^— or PO ₄ ^— . ]