TW201738281A - Coloring composition, colored cured film, display element, and solid-state imaging element - Google Patents

Abstract

A coloring composition that includes a (A) coloring agent, a (B) resin, and a (C) polymerizable compound, the (B) resin comprising a (b1) polymer having a cationic site and an anionic site in the same molecule. The (b1) polymer having a cationic site and an anionic site in the same molecule preferably includes a polymer having the repeating unit represented by formula (1). [In formula (1): R11 represents a hydrogen atom or a methyl group; R12 and R13 each independently represents a divalent organic group; (C1)+ represents -N+R14R15- or -P+R16R17-; R14 to R17 each independently represents a monovalent organic group; and (A1)- represents CO2 -, SO3 -, or PO4-).

Description

Coloring composition, coloring cured film, display element, solid-state imaging element, and polymer

The present invention relates to a coloring composition, a colored cured film, and a display element and a solid-state imaging element. More specifically, the present invention relates to a color liquid crystal display element and a solid which can be suitably used for manufacturing a transmissive or reflective type. A colored composition of a colored cured film used in an image pickup device, an organic electroluminescence (EL) display device, an electronic paper, or the like, a colored cured film formed using the colored composition, and a display member including the colored cured film And solid-state imaging elements.

In the production of a color filter using a coloring radiation-sensitive composition, the following method is known in which a pigment-dispersed color-sensing radiation-linear composition is applied onto a substrate and dried, and then the dried coating film is applied. The desired pattern shape is irradiated with radiation (hereinafter referred to as "exposure"), and development is performed to obtain pixels of respective colors (Patent Documents 1 to 2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is also known. Further, a method of obtaining a pixel of each color by an inkjet method using a pigment dispersion type colored resin composition is also known.

Research on dyes as coloring agents for color filters is being widely carried out. The reason for this is that when a dye is used as the colorant, it is considered that the color tone or the brightness of the display image at the time of image display can be improved due to the color purity of the dye itself or the vividness of the color tone. As such dyes, xanthene dyes, dipyrromethene dyes, quinophthalone dyes, triarylmethane dyes, quinoneimine dyes, and the like are known (for example, refer to the patent literature). 3 to Patent Document 7). In addition, in recent years, in order to obtain a further color thin film of a color filter, in order to obtain a color filter having a spectral characteristic equivalent to that of the prior art, it is being studied to increase the relative amount of the coloring agent in the pixel. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. 2011-122379 [Patent Document 6] International Publication No. 2011/152379 (Patent Document 7) Japanese Patent Laid-Open Publication No. 2012-155183

[Problems to be Solved by the Invention] However, the dye which is usually used in the coloring composition for forming a color filter is significantly insufficient in heat resistance due to its fragile pigment skeleton, and therefore has a large number of problems as a coloring composition for a color filter. It is difficult to put it into practical use. In addition, dyes are often mostly lacking in solubility in organic solvents, and coating film foreign matter is sometimes generated in the formed pixels. In addition, when the relative amount of the coloring agent such as a dye is increased in response to the demand for thin film formation in recent years, the relative amount of the component contributing to the curable property in the colored composition is reduced, so that the adhesion to the substrate may be caused. Not enough. Therefore, an object of the present invention is to provide a coloring composition which can form a colored cured film which is excellent in heat resistance and substrate adhesion and which is less likely to cause foreign matter of a coating film. Further, an object of the present invention is to provide a colored cured film formed using the colored composition, and a display element and a solid-state image sensor including the colored cured film. [Means to solve the problem]

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

That is, the present invention provides a colored composition comprising (A) a colorant, (B) a resin, and (C) a polymerizable compound, and (B) the resin contains (b1) a cationic moiety and an anionic property in the same molecule. The polymer of the part.

Moreover, the present invention provides a colored cured film formed using the colored composition, and a display element and a solid-state image sensor including the colored cured film. Here, the "coloring cured film" means a color pixel, a black matrix, a black spacer, or the like used in a display element or a solid-state image sensor.

Further, the present invention provides a polymer having a repeating unit represented by the following formula (1).

[Chemical 1]

[In the formula (1), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² and R ¹³ independently of each other represent a divalent organic group, and (C ¹ ) ⁺ represents -N ⁺ R ¹⁴ R ¹⁵ - or -P ⁺ R ¹⁶ R ¹⁷ -, R ¹⁴ to R ¹⁷ each independently represent a monovalent organic group, and (A ¹ ) ^- represents CO ₂ ^- , SO ₃ ^- or PO ₄ ^- ] [Effect of the invention]

By using the colored composition of the present invention, it is possible to form a colored cured film which is excellent in heat resistance and substrate adhesion and which is less likely to cause foreign matter of a coating film. Therefore, the colored composition of the present invention can be suitably used for producing a display element such as a color liquid crystal display element, an organic EL display element, or an electronic paper, a complementary metal oxide semiconductor (CMOS) image sensor, or the like. Solid-state imaging element.

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 agent (A) of the present invention can be used without particular limitation, and a color or a material can be appropriately selected depending on the use of a color filter or the like. Specifically, a pigment or a dye may be used as a coloring agent, and these coloring agents may be used alone or in combination of two or more. In particular, the present invention can form a colored cured film having excellent heat resistance even when a dye is contained as a coloring agent, and is preferable in this respect.

The pigment may, for example, be a compound classified into a pigment in a color index (CI, published by The Society of Dyers and Colourists), that is, a color index (CI) ) numbered pigments.

Red pigments such as CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264, CI Pigment Red 269; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green pigments such as Green 58, CI Pigment Green 59; CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 79, CI Pigment Blue 80 and other blue pigments; CI Pigment Yellow 83, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Yellow 215 and other yellow pigments; CI Pigment Orange 38 and other orange pigments; CI Pigment Purple 19, CI Pigment Violet 23 and other purple pigments.

In addition, the brominated diketopyrrolopyrrole pigment represented by the formula (Ic) of JP-A-2011-523433 may be used as the red pigment. In addition, JP-A-2001-081348, JP-A-2010-026334, JP-A-2010-191304, JP-A-2010-237384, and JP-A-2010- The lake pigment described in Japanese Laid-Open Patent Publication No. 2011-145346, and the like.

In the present invention, the pigment may be purified and used by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination of these methods. Further, these pigments may be used after the surface of the particles is modified by a resin as needed. Examples of the resin which is used to disperse the surface of the pigment particles include a medium resin described in JP-A-2001-108817, or a commercially available resin for dispersing various pigments. For the resin coating method of the surface of the carbon black, for example, the method described in JP-A-H09-71733, JP-A-H09-95625, JP-A-H09-124969, and the like can be employed. Further, the organic pigment may be used by refining the primary particles by so-called salt milling. For the method of salt milling, for example, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 8-179111 can be employed.

The dye is not particularly limited, and for example, a known dye can be used in addition to a compound classified into a dye (Dye) in a color index (C.I.; issued by The Society of Dyers and Colourists).

With regard to such a dye, examples of the structure of the chromophore include xanthene dye, triarylmethane dye, cyanine dye, anthraquinone dye, azo dye, dipyrromethene dye, and quinacridone. Dyes, coumarin dyes, pyrazolone dyes, quinoline dyes, nitro dyes, quinone imine dyes, phthalocyanine dyes, squaraine indole dyes, and the like. Further, an acid dye, a basic dye, and a nonionic dye can be suitably used. Here, the term "acid dye" as used herein means an ionic dye in which an anion portion is a chromophore, and an ionic dye which forms a salt with the anion portion is also regarded as an acid dye. In the present specification, the term "basic dye" means an ionic dye in which a cation moiety is a chromophore, and an ionic dye which forms a salt with the cation portion is also regarded as a basic dye. The term "nonionic dye" means a dye other than an acid dye or a basic dye.

As the xanthene dye, for example, CI Acid Red 52, CI Acid Red 87, CI Acid Red 92, CI Acid Red 289, CI Acid Red 388, and Synthesis Example 1 to Synthesis Example 3 of JP-A-2010-32999 can be used. a xanthene acid dye disclosed in Japanese Laid-Open Patent Publication No. 2011-138094; a xanthene basic dye such as CI basic violet 11; and a compound described in paragraph [0010] of JP-A-2013-053292, The compound represented by the formula (A1) to the formula (A6) described in the examples of JP-A-2013-100463, the paragraph [0038] to the paragraph [0043] and the paragraph of JP-A-2012-181505 [0048] The compound described in paragraph [0036] to paragraph [0038] of JP-A-2013-007032.

For the triarylmethane dye, for example, a triarylmethane acid dye such as CI Acid Blue 9; CI Basic Blue 7, International Publication No. 2010/123071, Japanese Patent Laid-Open No. 2011-116803, and Japanese Patent Laid-Open No. 2011- A triarylmethane basic dye described in Japanese Laid-Open Patent Publication No. 2011-133844, and Japanese Patent Laid-Open Publication No. JP-A No. 2001-011336, Japanese Patent Application Laid-Open No. Publication No. 2003-246935 Japanese Patent Laid-Open No. 2010-256598, Japanese Patent Laid-Open No. 2011-007847, Japanese Patent Laid-Open No. 2011-070172, Japanese Patent Laid-Open No. 2011-227408, and International Publication No. 2011/ Handbook No. 152379, Handbook of International Publication No. 2011/162217, Japanese Patent Laid-Open No. 2012-017425, Japanese Patent Laid-Open Publication No. 2012-037740, International Publication No. 2012/036085, Japanese Patent Laid-Open No. 2012-073291 Japanese Patent Laid-Open Publication No. 2012-083201, Japanese Patent Laid-Open Publication No. 2012-083652, Japanese Patent Laid-Open No. 2012-088615, Japanese Patent Laid-Open No. 2012-098522 The compound described in Japanese Patent Laid-Open Publication No. 2013-057053, the specification of the U.S. Patent Application Publication No. 2013/0141810, and the International Publication No. 2013/147099.

For the cyanine dye, for example, a cyanine acid dye such as CI Reactive Yellow 1; CI Basic Red 12, CI Basic Red 13, CI Basic Red 14, CI Basic Violet 7, CI Basic Violet 16, CI Alkaline Yellow 1, CI basic yellow 11, CI basic yellow 13, CI basic yellow 21, CI basic yellow 28, CI basic yellow 51 and the like cyanine dye; and Japanese Patent Laid-Open No. 2009-235392 The component (A-2) to the component (A-6) described in the examples, and the compound described in paragraph [0096] to [0108] of JP-A-2012-212089, Japanese Patent Laid-Open No. 2012-214718 The compound described in paragraphs [0054] to [0063] of the Japanese Patent Publication No. 2012-214719, and the compounds described in paragraph [0050] to [0054].

For the anthraquinone dye, for example, an acid dye such as CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, etc.; CI Reductive Blue 4, CI Disperse Red 60, CI Disperse Blue 56, CI Disperse Blue can be used. 60 蒽醌 蒽醌 蒽醌 蒽醌 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; 段落 段落 段落 段落 段落 段落 段落 段落 段落 段落 段落 段落 段落 段落 段落 段落 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 The compound described in JP-A-2013-210621, and the like.

For azo dyes, for example, CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI direct green 59, CI active yellow 2, CI active red 17, CI active red 120, CI active black 5, CI mordant red 7, CI mord yellow 5, CI mord black 7, CI direct green 28 and other azo acid Dye; CI basic blue 41, CI basic red 18; azo basic dyes described in Japanese Patent Laid-Open Publication No. 2011-145540; CI-dispersed orange 5, CI-dispersed red 58, CI-dissolved blue 165; An azo nonionic dye described in JP-A-2010-170073, JP-A-2010-170074, JP-A-2010-275531, and JP-A-2010-275533; Japanese Laid-Open Patent Publication No. 2005-510398, Japanese Patent Laid-Open No. Hei. No. 2005-226022, Japanese Patent Laid-Open No. Hei. No. 2007-212639, Japanese Patent Laid-Open No. 2010-152160, Japanese Patent Laid-Open No. 2010-170073, and Japanese Patent No. Opened the bulletin 2011-148993, Japan JP-A-2011-148994, JP-A-2011-148995, JP-A-2012-041461, JP-A-2012-062461, International Publication No. 2012/039361, Japanese Patent The pyridone azo dye described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. a diazo dye as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Mono azo dyes described in the publications, and the like. Japanese Patent Laid-Open No. Hei. No. 2005-274788, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Pyrazoles described in Japanese Patent Laid-Open Publication No. 2007-041050, Japanese Patent Laid-Open No. 2009-067748, Japanese Patent Laid-Open No. 2010-170116, and Japanese Patent Laid-Open Publication No. 2010-170117 A nitrogen dye; for example, paragraph [0058] to paragraph [0061] of JP-A-2007-293127, paragraph [0014] of JP-A-2011-219655, Japanese Patent Laid-Open No. 2013-145258, and the like Japanese Patent Publication No. 2010-150416, Japanese Patent Laid-Open No. 2010-152159, Japanese Patent Laid-Open No. 2010-170074, Japanese Patent Laid-Open No. 2011-016974, Japanese Patent The compound described in the specification of the Japanese Patent Application Laid-Open No. 2011-145540, and the specification of the Japanese Patent Application Publication No. 2013/0164681.

For the dipyrromethene dye, for example, a compound described in JP-A-2008-292970, and a polymerizable group-containing dipyrromethene compound described in JP-A-2011-180306 .

The quinophthalone dye can be, for example, those described in JP-A-H05-039269, JP-A-H06-220339, JP-A-H08-171201, and JP-A-2006-126649. The compound represented by the formula (2), the compound represented by the formula (1) described in JP-A-2010-250291, and the compound represented by the formula (1) described in JP-A-2013-209614. .

For the coumarin dye, for example, the compound described in the fourth embodiment of the Japanese Patent Laid-Open Publication No. Hei No. 4-179955, the compound represented by the formula (1) described in JP-A-2013-151668, and the Japanese Patent No. The compound represented by the formula (1) described in the above-mentioned Japanese Patent Publication No. 2014-044419, and the compound represented by the formula (1) described in JP-A-2014-044419.

For 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-2006-063171 can be used.

Examples of the quinoline dye include a quinoline acid dye such as C.I. Acid Yellow 3; a quinoline nonionic dye such as C.I. Solvent Yellow 33, C.I. Disperse Yellow 64.

The nitro dye may, for example, be a nitro acid dye such as C.I. Acid Yellow 1, C.I. Acid Orange 3 or a nitro nonionic dye such as C.I. Disperse Yellow 42.

Examples of the quinone imine dye include a quinone imine basic dye such as C.I. Basic Blue 3, C.I. Basic Blue 9.

For the phthalocyanine dye, for example, a phthalocyanine nonionic dye such as CI パッドブル 5 5; a compound described in JP-A-2004-233504, JP-A-2006-047497; and Japanese Patent Laid-Open No. 2007- The compound or the like described in paragraphs [0147] to [0155] of the publication No. 094181.

For the squarylium sulphate dye, for example, a compound described in JP-A-2012-013945, JP-A-2013-076926, and International Publication No. 2013/094827 can be used.

In addition to the above, various basic dyes described in Japanese Patent Laid-Open Publication No. 2007-503477; methic acid non-ionic dyes such as CI Solvent Yellow 179 and Disperse Yellow 201 or Japanese Patent Laid-Open Publication No. 2010-168531 The various nonionic dyes described in the third paragraph of the patent application or the fourth paragraph of the patent application.

In the present invention, the dyes can be appropriately selected and used, and from the viewpoint of improving heat resistance and substrate adhesion and suppressing generation of foreign matter of the coating film, it is preferably selected from xanthene dyes, triarylmethane dyes, and cyanine dyes. At least one of the group consisting of an anthraquinone dye, a dipyrromethene dye, and a phthalocyanine dye.

Further, in the present invention, a known dispersing aid may be further contained. The known dispersing aid may, for example, be a pigment derivative, and specific examples thereof include a copper phthalocyanine, a diketopyrrolopyrrole, and a sulfonic acid derivative of quinacridone.

(A) The content ratio of the coloring agent (A) is a black matrix or a black spacer which is excellent in brightness and heat resistance, and a black matrix and a black spacer, and the heat resistance and the substrate adhesion are improved, and the foreign matter of the coating film is suppressed. In general, the solid content of the coloring composition is from 5% by mass to 70% by mass, preferably from 10% by mass to 60% by mass. The solid component herein is a component other than the solvent described later.

- (B) Resin - The colored composition of the present invention needs to contain (b1) a specific polymer, and may further contain a binder resin or a dispersant different from (b1). Hereinafter, (b1) a 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 (b1) specific polymer does not include a salt having no cationic portion, such as sodium polystyrene sulfonate, and has only an anionic portion, a salt of a counter cation, or no anionic portion. a salt of a polymer having a cationic moiety and a counter anion. (b1) The specific polymer preferably has a cationic portion and an anionic portion at non-adjacent positions in the same molecule, and is preferably not bonded to a positively charged atom in the cationic portion. Dissociated hydrogen atoms.

The (b1) specific polymer of the present invention preferably contains an ethylenically unsaturated monomer having a cationic site and an anionic site (hereinafter also referred to as "unsaturated monomer" (the following is also known as an unsaturated monomer). The polymer of the monomer of b1-1)") is preferably a polymer selected from the group consisting of 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 of them.

[Chemical 2]

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

[Chemical 3]

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

Examples of the divalent organic group of R ¹² , R ¹³ , R ²² and R ²³ include a divalent hydrocarbon group, a group obtained by combining a divalent hydrocarbon group and a linking group containing a carbon atom and an atom other than a hydrogen atom, or the like. A group in which a part of a hydrogen atom of a group is substituted with a halogen group. Further, examples of the halogen group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of such a divalent organic group include an alkanediyl group having 1 to 10 carbon atoms, an extended aryl group having 6 to 20 carbon atoms, an alkylene alkanediyl group having 7 to 20 carbon atoms, or a carbon number of 1 selected. At least one of the alkanediyl group of ～10 and the aryl group of 6 to 20 carbon atoms is selected from the group consisting of -O-, -S-, -COO-, -CONR ^b - (R ^b represents a hydrogen atom or a carbon number of 1 to A group in which at least one of 8 alkyl groups and -SO ₂ - is combined.

The alkanediyl group may be a straight chain or a branched chain, and examples thereof include a methylene group, an ethylidene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, and a propane-1,2- Diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl , pentane-1,4-diyl, pentane-1,5-diyl, hexane-1,5-diyl, hexane-1,6-diyl, octane-1,8-diyl An alkanediyl group having 1 to 10 carbon atoms such as a decane-1,10-diyl group. Examples of the aryl group include a phenyl group having 6 to 10 carbon atoms such as a phenyl group, a naphthyl group, a phenylene group, and a fluorene group. The arylalkylene diradical group is a divalent group obtained by combining an aryl group and an alkanediyl group, and examples thereof include a phenylmethylene group, a phenylene dimethylene group, and a phenyltrimethylene group. a phenylene C _1-6 alkanediyl group such as a phenyltetramethylene group, a phenylpentamethylene group or a phenylhexamethylene group.

Further, at least one selected from the group consisting of an alkanediyl group having 1 to 10 carbon atoms and an exoaryl group having 6 to 20 carbon atoms is selected from the group consisting of -O-, -S-, -COO-, -CONR ^b - (R ^b A group in which at least one of a hydrogen atom or an alkyl group having 1 to 8 carbon atoms and -SO ₂ - is preferably selected is an alkanediyl group having a carbon number of 1 to 10 and a carbon number of 6 to 20 a group in which at least one of the aryl groups is combined with at least one selected from the group consisting of -O-, -COO-, and -SO ₂ -, more preferably an alkanediyl group having a carbon number of 1 to 10 and carbon At least one of the number of 6 to 20 aryl groups is a combination of at least one selected from the group consisting of -O- and -SO ₂ -. Further, specific examples of the alkyl group having 1 to 8 carbon atoms of R ^b include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, and a third group. Butyl, hexyl, heptyl, octyl and the like.

Wherein, R ¹² is preferably a divalent organic group and R ²² is alkanediyl group having a carbon number of 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, or selected from carbon and alkanediyl group having 1 to 10 More preferably, at least one of the 6 to 20 exoaryl groups is a combination of at least one selected from the group consisting of -O-, -S-, -COO-, -CONR ^b - and -SO ₂ -, more preferably a aryl group having 6 to 10 carbon atoms, or at least one selected from the group consisting of an alkanediyl group having 1 to 8 carbon atoms and an exoaryl group having 6 to 10 carbon atoms selected from the group consisting of -O-, -COO-, -CONR A group in which at least one of ^b - and -SO ₂ - is combined. Further, at least one selected from the group consisting of an alkanediyl group having 1 to 10 carbon atoms and an extended aryl group having 6 to 20 carbon atoms is selected from the group consisting of -O-, -S-, -COO-, -CONR ^b - and Among the groups in which at least one of -SO ₂ - is combined, it is preferred that the alkanediyl group having 1 to 10 carbon atoms is bonded to (C ¹ ) ⁺ or (A ² ) ^- . Further, the divalent organic group of R ¹³ and R ²³ is preferably an alkanediyl group having 1 to 10 carbon atoms, an extended aryl group having 6 to 20 carbon atoms or an alkylene alkanediyl group having 7 to 20 carbon atoms, more preferably The alkanediyl group having 1 to 5 carbon atoms is more preferably a methylene group, an ethyl group, a propane-1,3-diyl group or a pentane-1,5-diyl group.

(C ¹ ) ⁺ in the formula (1) is a divalent linking group represented by -N ⁺ R ¹⁴ R ¹⁵ - or -P ⁺ R ¹⁶ R ¹⁷ -, and (C ² ) ⁺ in the 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, the monovalent organic group of R ¹⁴ to R ¹⁷ and R ²⁴ to R ²⁹ may be a monovalent hydrocarbon group, and the monovalent hydrocarbon group may be a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. Any of them. Further, the monovalent aliphatic hydrocarbon group may be in any of a linear form and a branched form, and the monovalent aliphatic hydrocarbon group and the monovalent alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, the unsaturated bond group may have an unsaturated bond at any position within the molecular chain and at the end of the molecular chain, and may have an unsaturated bond of an unsaturated hydrocarbon group at any position. Here, the "alicyclic hydrocarbon group" in the present specification is a concept excluding an aliphatic hydrocarbon group having no cyclic structure. In addition, the "alicyclic hydrocarbon group" and the "aromatic hydrocarbon group" in the present specification are the following concepts: not only a group containing only a ring structure but also a group further substituted with a divalent aliphatic hydrocarbon group on the ring structure. As long as the structure contains 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 invention. The position and the number of the substituent are arbitrary, and in the case of having two or more substituents, the substituents may be the same or different. The substituent may, for example, be a halogen group, a cyano group, a decyl group, a nitro group, a trialkylalkyl group, an alkoxy group, an aryloxy group or a heterocyclic group. Examples of the halogen group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The monovalent aliphatic hydrocarbon group may, for example, be an alkyl group, an alkenyl group or an alkynyl group. The carbon number of the aliphatic hydrocarbon group is preferably from 1 to 30, more preferably from 1 to 20, still more preferably from 1 to 12. 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 second butyl group, a third butyl group, a hexyl group, a heptyl group, an octyl group, and an anthracene group. Base, fluorenyl, undecyl, 1-methylindenyl, dodecyl, 1-methylundecyl, 1-ethylindenyl, tridecyl, tetradecyl, third - dodecyl, pentadecyl, 1-heptyloctyl, hexadecyl, octadecyl, and the like. Specific examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1,3-butadienyl group, and a 1-pentenyl group. -pentenyl, 1-hexenyl, 2-ethyl-2-butenyl, 2-octenyl, (4-vinyl)-5-hexenyl, 2-dodecenyl and the like. Further, specific examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-pentynyl group, a 3-pentynyl group, a 1-hexynyl group, and a 2-ethyl-2 group. -butynyl, 2-octynyl, (4-ethynyl)-5-hexynyl, 2-dodecynyl and the like.

The monovalent alicyclic hydrocarbon group may, for example, be a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged cyclic hydrocarbon group, a spirohydrocarbyl group or a cyclic terpene group. The carbon number of the aliphatic hydrocarbon group is preferably from 3 to 30, more preferably from 3 to 20, still more preferably from 3 to 12. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a tert-butylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of the cycloalkenyl group include, for example, 1-cyclohexenyl and the like. Further, specific examples of the condensed polycyclic hydrocarbon group include a tricyclodecanyl group, a decahydro-2-naphthyl group, and an adamantyl group, and specific examples of the bridged cyclic hydrocarbon group include a tricyclic ring [5.2.1.0 ^{2, 6} ] decane-8-yl, pentacyclopentadecyl, isobornyl, dicyclopentenyl, tricyclopentenyl, and the like. Further, examples of the spirohydrocarbyl group include a monovalent group obtained by removing one hydrogen atom from spiro[3,4]heptane or spiro[3,4]octane, and examples of the cyclic alkene group include, for example, A monovalent group obtained by removing one hydrogen atom from p-menthane, thujone, carane, or the like.

The monovalent aromatic hydrocarbon group may, for example, be an aryl group or an aralkyl group. The carbon number of the aromatic hydrocarbon group is preferably from 6 to 20, more preferably from 6 to 14, more preferably from 6 to 10. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a stretched biphenyl group, a fluorenyl group, and a 9-fluorenyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, and the like. Benzyl and the like.

From the viewpoints of ease of obtaining raw materials and heat resistance, (C ¹ ) ⁺ in the formula (1) is preferably -N ⁺ R ¹⁴ R ¹⁵ -, and (C ² ) ⁺ in the formula (2) It 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. Preferred examples of the groups are as described above, and more preferably an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms and a phenyl group. .

(A ¹ ) ^- in the formula (1) represents CO ₂ ^- , SO ₃ ^- or PO ₄ ^- , and is preferably CO ₂ ^- , SO ₃ ^- or the like from the viewpoints of easiness of obtaining raw materials and heat resistance. Good for SO ₃ ^- . Represented by two - N or ^{-C (= O) - - SO} 2 of formula (2) (A ^{2) -} as -OP (= O) (- O -) O -, - SO 2 N - SO 2 divalent linking group, to obtain the viewpoint of heat resistance and easiness of raw material, preferable are -OP (= O) (- O -) O- or -SO ₂ N ^- SO ₂ ^-, more preferably -OP ( =O)(-O ^- )O-.

In the case where the (b1) 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 may have other repeats. unit. In this case, the content of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) in the polymer is preferably from 3% by mass to 90% by mass, more preferably 5% by mass. 60% by mass, and more preferably 10% by mass to 40% by mass.

The monomer which forms the repeating unit represented by the formula (1) is exemplified by N-(meth)acrylomethoxyethyl-N,N-dimethylammonium-α-N-ethylcarboxylate, N, N-Dimethyl-N-(3-sulfonylpropyl)-2-(methylpropenyloxy)ethane-1-ammonium or the like. In addition, a reaction product of a monomer synthesized by the method described in JP-A-H09-095474 or a phosphine having a polymerizable unsaturated group and a sultone may be used. Examples of the monomer forming the repeating unit represented by the formula (2) include 2-(meth)acryloxyethylphosphonium choline and the like.

The monomer which forms the polymer which has the repeating unit represented by Formula (1), and the other repeating unit which can be contained in the polymer of the repeating unit represented by Formula (2) can be exemplified as the (b2) adhesive resin mentioned later. Unsaturated monomer (b2-1), unsaturated monomer (b2-2). Further, as the polymer having the repeating unit represented by the formula (2), Lipidure (registered trademark, manufactured by Nippon Oil Co., Ltd.) or the like can be used.

(b1) A known method can be employed for the synthesis reaction of the specific polymer, and examples thereof include anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. (b1) The molecular weight of the specific polymer is preferably from 1,000 to 100,000, more preferably from 3,000 to 50,000, by weight average molecular weight (Mw) as measured by Gel Permeation Chromatography (GPC). Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the (b1) specific polymer is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, Mw and Mn here are the polystyrene-converted number average molecular weight measured by GPC (dissolving solvent: tetrahydrofuran).

Next, the binder resin and the dispersing agent which can be contained in the colored composition of the present invention will be described. The coloring composition of the present invention preferably contains (b2) a binder resin together with (b1) a specific polymer from the viewpoint of storage stability and developability, wherein the (b1) specific polymer is excluded ). (b2) The binder resin is not particularly limited, and is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. In particular, a polymer having a carboxyl group (hereinafter also referred to as a "carboxyl group-containing polymer") is preferably an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as "unsaturated monomer" (hereinafter also referred to as "unsaturated monomer"). B2-1)") a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as "unsaturated monomer (b2-2)"). The binder resin may be used alone or in combination of two or more.

Examples of the unsaturated monomer (b2-1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono[2-(methyl)acryloxyethyl)ester, and ω-carboxyl polymerization. Caprolactone mono(meth)acrylate, p-vinylbenzoic acid, and the like. The unsaturated monomer (b2-1) may be used alone or in combination of two or more.

Further, the unsaturated monomer (b2-2) may, for example, be N-phenylmaleimide or N-cyclohexylmaleimine-like N-substituted maleimide; styrene, α- Methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, anthracene-like aromatic vinyl compound;

Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate Benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene Alcohol (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 , (cyclo) (5. ^{6 2, 6} ] decane-8-yl ester, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, (meth) acrylate - 4-hydroxyphenyl ester, ethylene oxide modified (meth) acrylate of p-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, 3-[(Meth) propylene methoxymethyl] oxetane, 3-[(meth) propylene methoxymethyl]-3-ethyl oxetane (meth) Acrylate;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)-3 a vinyl oxetane-like vinyl ether; having a terminal of a polymer molecular chain such as polystyrene, poly(methyl) methacrylate, poly(methyl) methacrylate, or polyoxyalkylene A mono (meth) acrylonitrile-based macromonomer or the like. The unsaturated monomer (b2-2) may be used alone or in combination of two or more.

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 from 5% by mass to 50% The mass% is further preferably 10% by mass to 40% by mass. By copolymerizing the unsaturated monomer (b2-1) in such a range, a coloring composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) include, for example, Japanese Patent Laid-Open No. Hei. Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The copolymer disclosed in Japanese Laid-Open Patent Publication No. 2004-101728 or the like.

In the present invention, for example, Japanese Patent Laid-Open No. Hei 5-19467, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth)acrylonyl group in a side chain as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. Adhesive resin. In the colored composition of the present invention, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a side chain is used as the (b2) binder resin, and a highly sensitive color can be obtained. The composition, in addition, can improve the hardenability of the coating film, and is preferable in this respect.

(b2) The binder resin can be produced by a known method, for example, by the Japanese Patent Laid-Open Publication No. 2003-222717, the Japanese Patent Laid-Open No. 2006-259680, the International Publication No. 2007/029871, and the like. A method is disclosed to control its structure or Mw, Mw/Mn.

In the (b2) binder resin of the present invention, the Mw measured by GPC is usually from 1,000 to 100,000, preferably from 3,000 to 50,000. By setting such an aspect, heat resistance can be further improved, and generation of foreign matter can be effectively suppressed. Further, the (b2) binder resin of the present invention preferably has an Mw/Mn of from 1.0 to 5.0, more preferably from 1.0 to 3.0.

In the case where the colored composition of the present invention contains a pigment as the coloring agent (A), it is preferred to contain (b3) a dispersing agent (wherein the (b1) specific polymer and (in the viewpoint of storage stability) B2) Except for the binder resin) as the (B) resin. (b3) The dispersant may, for example, be a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylidene ether dispersant, or a polyoxyethylidene phenyl ether dispersion. Agent, polyethylene glycol diester dispersant, sorbitan fatty acid ester dispersant, polyester dispersant, acrylic dispersant, and the like.

Such (b3) dispersing agents are commercially available, for example, Disperbyk-2000, Disperbyk-2001, BYK as an acrylic dispersing agent, respectively. )-LPN6919, BYK-LPN21116 (above, BYK Chemie), etc.; Disperbyk-161, Dispa, as a urethane dispersant Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk- 182 (above is manufactured by BYK Chemie), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), etc.; Sonupa as a polyethyleneimine dispersant Solsperse 24000 (manufactured by Lubrizol Co., Ltd.); Ajisper PB821, Ajisper PB822, Ajispa (as a polyester dispersant) Ajisper) PB880, Ajisper PB881 (above is Ajinomoto Precision Technology) (Ajinomoto Fine-techno) (shares) Co., Ltd.), and BYK (BYK) -LPN21324 (BYK-Chemie (BYK Chemie) manufactured). Among them, an acrylic dispersant having an (N-substituted) amine group is preferred.

In the present invention, the content of the (b1) specific polymer is usually from 1 part by mass to 200 parts by mass, preferably from 5 parts by mass to 100 parts by mass, more preferably 10 parts by mass, per 100 parts by mass of the (A) coloring agent. ~50 parts by mass. By setting such a state, the storage stability of the colored composition is improved, and not only the heat resistance of the cured film and the substrate adhesion can be improved, but also the generation of foreign matter of the coating film can be effectively suppressed. Further, the content of the (b2) binder resin is usually 10 parts by mass to 1,000 parts by mass, preferably 20 parts by mass to 500 parts by mass, more preferably 50 parts by mass to 200 parts by mass based on 100 parts by mass of the (A) coloring agent. Parts by mass. By setting such an aspect, the alkali developability, the storage stability of the colored composition, the pattern shape, and the chromaticity characteristics can be further improved, and the occurrence of precipitates or foreign matter of the coating film can be suppressed. Further, the content of the (b3) dispersant is usually from 1 part by mass to 100 parts by mass, preferably from 5 parts by mass to 70 parts by mass, more preferably from 10 parts by mass to 50% by mass based on 100 parts by mass of the (A) coloring agent. Share.

- (C) Polymerizable Compound - The polymerizable compound in the present invention means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxyheteropropyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the (C) polymerizable compound is preferably a compound having two or more (meth)acryl fluorenyl groups or a compound having two or more N-alkoxymethylamino groups. (C) The polymerizable compound may be used alone or in combination of two or more.

Specific examples of the compound having two or more (meth)acryl fluorenyl groups include a reaction of an aliphatic polyhydroxy compound with (meth)acrylic acid [polyfunctional (meth) acrylate], and modification by caprolactone. Reaction of a polyfunctional (meth) acrylate, an alkylene oxide-modified polyfunctional (meth) acrylate, a hydroxyl group-containing (meth) acrylate with a polyfunctional isocyanate [polyfunctional (methyl) A urethane urethane], a reactant of a hydroxyl group-containing (meth) acrylate and an acid anhydride [a polyfunctional (meth) acrylate having a carboxyl group], and the like.

Here, examples of the aliphatic polyhydroxy compound include a divalent aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. More than an aliphatic polyhydroxy compound. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and Pentaerythritol penta (meth) acrylate, glycerin dimethacrylate, and the like. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include an anhydride of a dibasic acid such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and pyromellitic anhydride and biphenyl tetra A tetrabasic acid dianhydride such as a carboxylic acid dianhydride or a benzophenone tetracarboxylic dianhydride.

In addition, the polyfunctional (meth) acrylate modified by the caprolactone is, for example, a compound described in paragraphs [0015] to [0018] of JP-A-11-44955. The alkylene oxide-modified polyfunctional (meth) acrylate may be exemplified by at least one modified bisphenol A di(meth) acrylate selected from the group consisting of ethylene oxide and propylene oxide. At least one modified isocyanuric acid tri(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, and at least one modified trimycyl group selected from the group consisting of ethylene oxide and propylene oxide a propane tri(meth) acrylate, at least one modified pentaerythritol tri(meth) acrylate selected from the group consisting of ethylene oxide and propylene oxide, selected from the group consisting of ethylene oxide and propylene oxide At least one modified pentaerythritol tetra(meth)acrylate, at least one modified dipentaerythritol penta (meth) acrylate selected from the group consisting of ethylene oxide and propylene oxide, selected from ethylene oxide and At least one modified dipentaerythritol hexa(meth)acrylate or the like of propylene oxide.

Further, examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. Further, the melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or a phenyl-substituted triazine ring as a basic skeleton, and also includes melamine, benzoguanamine or the like. The concept of structural condensates. 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'-tetrakis(alkoxymethyl)benzoguanamine, N,N,N',N'-tetrakis(alkoxymethyl)glycolil and the like.

Among these polymerizable compounds, a reaction product of a tribasic or higher aliphatic polyhydroxy compound and (meth)acrylic acid [polyfunctional (meth) acrylate], a polyfunctional modified by caprolactone is preferred (A) Acrylate, polyfunctional (meth) acrylate urethane, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N'', N''-six Alkoxymethyl)melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoguanamine. The trivalent or higher aliphatic polyhydroxy compound is excellent in the strength of the colored layer and the surface smoothness of the colored layer, and not only the heat resistance of the cured film and the substrate adhesion but also the foreign matter of the coating film are less likely to occur. Among the reactants (polyfunctional (meth) acrylate) of (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like are preferable. Among the polyfunctional (meth) acrylates of a carboxyl group, a reaction product of pentaerythritol triacrylate and succinic anhydride, a reaction product of dipentaerythritol pentaacrylate and succinic anhydride is particularly preferred.

The content of the (C) polymerizable compound of the present invention is preferably from 10 parts by mass to 1,000 parts by mass, more preferably from 20 parts by mass to 800 parts by mass, even more preferably 100 parts by mass, based on 100 parts by mass of the (A) coloring agent. ~500 parts by mass. By setting it as such a pattern, it is possible to form a black matrix or a black spacer which is excellent in heat resistance and a light-shielding property. Further, not only the heat resistance of the cured film and the substrate adhesion can be improved, but also the generation of foreign matter of the coating film can be effectively suppressed.

- Photopolymerization initiator - The coloring composition of the present invention may contain a photopolymerization initiator. Thereby, the coloring composition can be imparted with radiation. The photopolymerization initiator used in the present invention is a compound which generates an active species which can initiate polymerization of (C) a polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray. The photopolymerization initiator may be used alone or in combination of two or more.

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an O-mercaptoquinone compound, a phosphonium salt compound, and a benzoin compound. A benzophenone-based compound, an α-diketone-based compound, a polynuclear oxime-based compound, a diazo-based compound, a quinone sulfinate-based compound, or a phosphonium salt-based compound. Among them, at least one selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, and an O-mercaptoquinone compound is preferable.

Specific examples of the thioxanthone-based compound in the preferred photopolymerization initiator of the present invention include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthene. Ketone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Ketyl ketone and the like.

Further, specific examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one and 2-benzyl-2- Dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Morpholinylphenyl)butan-1-one and the like.

Further, specific examples of the biimidazole-based 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',5,5'-tetraphenyl-1,2'-biimidazole and the like.

Further, in the case where a biimidazole-based compound is used as the photopolymerization initiator, it is preferred to use a hydrogen donor in combination in terms of improving the sensitivity. The term "hydrogen donor" as used herein refers to a compound which can supply a hydrogen atom to a radical generated by a biimidazole compound by exposure. Examples of the hydrogen donor include a mercaptan hydrogen donor such as 2-mercaptobenzothiazole or 2-mercaptobenzoxazole; 4,4'-bis(dimethylamino)benzophenone, 4,4 An amine-based hydrogen donor such as '-bis(diethylamino)benzophenone. In the present invention, the hydrogen donor may be used alone or in combination of two or more. In terms of further improving the sensitivity, it is preferred to combine one or more thiol-based hydrogen donors with one or more amine-based hydrogen donors. use.

In addition, specific examples of the triazine-based compound include the compounds described in paragraphs [0063] to [0065] of JP-A-57-57096, and JP-A-2003-238898.

Further, specific examples of the O-mercapto fluorene-based compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoguanidinopurine), Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), ethyl ketone, 1 -[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), Ethylketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene}- 9H-carbazol-3-yl]-, 1-(O-ethylindenyl) and the like. Commercial products of O-mercapto lanthanide compounds can also be used: NCI-831, NCI-930 (above is manufactured by ADEKA Co., Ltd.), OXE-03, OXE-04 (above is BASF ( BASF) company manufacturing) and so on.

In the case of using a photopolymerization initiator other than a biimidazole-based compound such as an acetophenone-based compound, a sensitizer may be used in combination. Examples of such a sensitizer include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-diethyl. Aminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis ( 4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamine Base) Chalcone and the like.

In the present invention, the content of the photopolymerization initiator is preferably from 0.01 part by mass to 120 parts by mass, and more preferably from 1 part by mass to 100 parts by mass, per 100 parts by mass of the (C) polymerizable compound. By setting such an aspect, it is possible to suppress not only the generation of foreign matter of the coating film but also the curability and film properties (heat resistance and substrate adhesion).

- Solvent - The colored composition of the present invention contains the components (A) to (C) and other components added arbitrarily, and is usually prepared by mixing an organic solvent and forming a liquid composition. The organic solvent can be appropriately selected and used as long as it disperses or dissolves the components (A) to (C) or other components constituting the colored composition and does not react with the components and has moderate volatility. The solvent may be used alone or in combination of two or more.

Examples of such an organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Alcohol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl Ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. Glycol monoalkyl ether;

An alkyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, cyclohexanol, etc. (cyclo)alkyl alcohol; keto alcohol 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 single Ethyl acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc. Alkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other cyclic ether; methyl ethyl ketone, cyclohexanone, 2- a ketone such as heptanone or 3-heptanone;

Diacetate such as propylene glycol diacetate, 1,3-butanediol diacetate or 1,6-hexanediol diacetate; methyl 3-methoxypropionate, 3-methoxy Alkoxylates such as ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate Carboxylic acid ester; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, N-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2-sided oxygen A fatty acid alkyl ester such as ethyl butyrate; an aromatic hydrocarbon such as toluene or xylene; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. Indoleamine or indoleamine.

Among these solvents, from the viewpoints of solubility, pigment dispersibility, coatability, and the like, it is preferably selected from (poly)alkylene glycol monoalkyl ethers and (poly)alkylene glycol monoalkyl groups. At least one of ether acetates.

The content of the solvent is not particularly limited, and the total concentration of each component excluding the solvent of the coloring composition is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass. By setting such an aspect, a colorant dispersion having good dispersibility and stability and a coloring composition having good coatability can be obtained.

- Additive - The coloring composition of the present invention may contain various additives as needed. Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); a surfactant such as a fluorine-based surfactant or an anthrone-based surfactant; and a vinyl group; Trimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Baseline, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3- a adhesion promoter such as chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane or 3-mercaptopropyltrimethoxydecane; 2,2-thiobis(4-methyl-) Antioxidant such as 6-t-butylphenol), 2,6-di-tert-butylphenol; 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzene And ultraviolet absorbers such as triazole and alkoxybenzophenone; anticoagulation such as sodium polyacrylate Malonate, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentane Residue improver such as alcohol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono [2-(methyl) a developing improver such as propylene methoxyethyl ester, phthalic acid mono [2-(methyl) propylene oxyethyl ester], ω-carboxy polycaprolactone mono (meth) acrylate Wait.

Method for Producing Colored Composition The colored composition of the present invention can be produced by a suitable method, and the preparation method thereof can be, for example, mixed by mixing the components (A) to (C) with a solvent or any other component added arbitrarily. And prepared. In the case where (A) the colorant contains a pigment, it is preferably a method prepared by using a pigment such as a bead mill, a roll mill or the like in a solvent in the presence of a (b3) dispersant. And (b2) a part of the binder resin is mixed and dispersed while being pulverized to form a pigment dispersion liquid, and then (b1) a specific polymer and (C) a polymerizable compound are added to the pigment dispersion liquid. The (b2) binder resin, the photopolymerization initiator, and further an additional solvent or other components are required to be mixed.

Color-cured film and method of forming the same The following describes a colored cured film used in a color filter constituting a display element or a solid-state image sensor, and a method of forming the same. Further, the colored cured film of the present invention can be formed using the colored composition of the present invention, in other words, contains (A) a colorant and (b1) a polymer having a cationic site and an anionic site in the same molecule. Regarding the method of manufacturing a color filter, the first method is as follows. First, a light shielding layer (black matrix) is formed on the surface of the substrate in such a manner as to separate the portions where the pixels are formed. Then, a liquid composition of, for example, a blue radiation sensitive coloring composition of the present invention is applied onto the substrate, and then pre-baked to evaporate the solvent to form a coating film. Then, after exposing the coating film to the mask, development is carried out using an alkaline developing solution, and the unexposed portion of the 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 array.

Then, each of the radiation-sensitive coloring compositions of green or red is used, and the coating, prebaking, exposure, development, and post-baking of the respective radiation-sensitive coloring compositions are performed in the same manner as described above, sequentially on the same substrate. A green pixel array and a red pixel array are formed. Thereby, a color filter in which a pixel array of three primary colors of blue, green, and red is disposed on the substrate can be obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the order.

The black matrix can be formed by forming a desired pattern by a metal film such as chromium or the like which is formed by sputtering or vapor deposition using a photolithography method, or using a radiation-sensitive linear dispersion-dispersed coloring agent. The coloring composition is formed in the same manner as in the case of forming the pixel.

Examples of the substrate used for forming the color filter include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimide. For these substrates, an appropriate pretreatment such as chemical treatment such as a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum vapor deposition may be performed in advance.

When the radiation sensitive coloring composition is applied onto a substrate, 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 may be employed. A suitable coating method such as a method is particularly preferably a spin coating method or a slit die coating method.

The prebaking is usually carried out at 70 ° C to 110 ° C for about 1 minute to 10 minutes.

The coating thickness is usually from 0.6 μm to 8 μm, preferably from 1.2 μm to 5 μm, in terms of the film thickness after drying.

Examples of the light source for forming radiation selected from at least one of a pixel and a black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure mercury lamp. Such as light source or argon ion laser, Yttrium Aluminum Garnet (YAG) laser, XeCl excimer laser, nitrogen laser and other laser sources. The exposure light source can also use a Light Emitting Diode (LED). Radiation having a wavelength in the range of 190 nm to 450 nm is preferred.

The exposure amount of the radiation is usually preferably from 10 J/m ² to 10,000 J/m ² . Further, the alkaline developing solution is preferably, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4.0]- An aqueous solution of 7-undecene or 1,5-diazabicyclo-[4.3.0]-5-nonene.

In the alkaline developing solution, for example, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount. Further, after alkali development, water washing is usually carried out. As the development treatment method, a shower development method, a spray development method, a dip development method, a liquid coating method, or the like can be applied. The developing conditions are preferably normal temperature and 5 seconds to 300 seconds.

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

In the second method of producing a color filter, a method of obtaining pixels of respective colors by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. In this method, a partition wall having a light-shielding function is first formed on the surface of the substrate. Then, a liquid composition of, for example, a blue thermosetting coloring composition is ejected by the ink jet device in the formed partition wall, and then prebaked to evaporate the solvent. Then, the coating film is exposed as necessary, and then post-baked to be cured to form a blue pixel pattern.

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

Further, since the partition wall not only functions as a light-shielding function but also functions to prevent color mixing of the thermosetting coloring composition of each color discharged into the block, it is compared with the black matrix used in the first method. The film thickness is thicker. Therefore, the partition wall is usually formed using a black radiation linear composition. The substrate or the source of radiation used in forming the color filter, and the method or conditions of prebaking or postbaking are the same as those of the first method. Thus, the film thickness of the pixel formed by the inkjet method is the same as the height of the partition wall.

After the protective film is formed on the pixel pattern thus obtained, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer is formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, and may be formed into a light-shielding spacer (black spacer). In this case, a radiation-sensitive coloring composition in which a black coloring agent is dispersed may be used, and the coloring composition of the present invention may also be suitably used to form the black spacer.

The colored composition of the present invention can also be suitably used for forming any colored cured film of each color pixel, black matrix, black spacer, or the like used in the color filter. The color filter having the colored cured film of the present invention thus formed is extremely high in brightness and color purity, and thus is used in a color liquid crystal display element, a color image pickup element, a color sensor, an organic EL display element, an electronic paper, or the like. Extremely useful. Further, the display element to be described later may have at least one color curing film formed using the coloring composition of the present 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, electronic paper, and the like. The color liquid crystal display element having the colored cured film of the present invention may be of a transmissive type or a reflective type, and may have an appropriate structure. For example, a color filter may be formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is disposed, and the substrate for driving and the substrate on which the color filter is formed pass through the liquid crystal layer. And relative. Further, a structure in which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and oxidation of indium tin oxide (ITO, Indium Tin Oxide, tin-doped) may be employed. The substrate of the indium) electrode or indium zinc oxide (IZO, Indium Zinc Oxide, a mixture of acid indium and zinc oxide) is opposed to each other via the liquid crystal layer. The latter structure has an advantage that the aperture ratio can be particularly increased, and a bright and high-definition liquid crystal display element can be obtained. Further, in the case of employing the latter structure, the black matrix or the black spacer may be formed on the substrate side on which the color filter is formed and on either side of the substrate side on which the ITO electrode or the IZO electrode is formed.

A color liquid crystal display device including the colored cured film of the present invention may include a backlight unit having a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). Examples of the white LED include a white LED in which a red LED, a green LED, and a blue LED are combined and white light is obtained by color mixing, and a blue LED, a red LED, and a green light-emitting phosphor are combined and white is obtained by color mixing. A white LED that combines a blue LED, a red illuminating phosphor, and a green illuminating phosphor to obtain a white LED with white light by color mixing, and obtains a white color by mixing a blue LED with a YAG phosphor. a white LED that combines a blue LED, an orange illuminating phosphor, and a green illuminating phosphor to obtain a white LED with white light by mixing colors, and an ultraviolet LED, a red luminescent phosphor, a green luminescent phosphor, and A white LED or the like in which blue luminescent phosphors are combined and white light is obtained by color mixing.

In a color liquid crystal display device having the colored cured film of the present invention, a twisted nematic (TN) type, a super twisted nematic (STN) type, and an in-plane switching (In-Planes Switching, IPS) can be applied. A suitable liquid crystal mode such as a Vertical Alignment (VA) type or an Optically Compensated Birefringence (OCB) type.

The organic EL display device having the colored cured film of the present invention can have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242 can be cited. In addition, the electronic paper provided with the cured film of the present invention can have an appropriate structure, and for example, the structure disclosed in Japanese Laid-Open Patent Publication No. 2007-41169 can be cited.

Solid-state imaging device The solid-state imaging device of the present invention comprises the colored cured film of the present invention. Further, the solid-state image sensor of the present invention can adopt an appropriate structure. For example, in one embodiment, color separation or color reproducibility can be produced by forming a color pixel (coloring cured film) on a semiconductor substrate such as a CMOS substrate by using the coloring composition of the present invention by the same operation as described above. Excellent solid-state imaging device. [Examples]

Hereinafter, embodiments of the present invention will be more specifically described by way of examples. However, the invention is not limited to the following examples.

<Synthesis of Resin> Synthesis Example 1 100 parts by mass of propylene glycol monomethyl ether acetate was added to a flask equipped with a condenser and a stirrer, and nitrogen substitution was performed. Heating to 80 ° C, at this temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, and 5 parts by mass of benzyl methacrylate were added dropwise over 1 hour. 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid A mixed solution of mono(2-propenyloxyethyl)ester and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was polymerized for 2 hours while maintaining the temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour, whereby a resin solution (B-1) (solid content concentration: 33% by mass) was obtained. The obtained resin had an Mw of 12,200 and an Mn of 6,500. This resin corresponds to (b2) a binder resin.

Synthesis Example 2 To a flask equipped with a condenser and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was added and replaced with nitrogen. The mixture was heated to 80 ° C, and 100 parts by mass of propylene glycol monomethyl ether acetate, 35 parts by mass of a compound represented by the following formula (Bet-1), and 13 parts by mass of methacrylic acid were added dropwise at this temperature for 1 hour. 6.5 parts by mass of styrene, 3.2 parts by mass of benzyl methacrylate, 9.8 parts by mass of 2-hydroxyethyl methacrylate, 15 parts by mass of 2-ethylhexyl methacrylate, and 7.8 parts by mass N-phenylmaleimide, 9.7 parts by mass of mono(2-propenyloxyethyl) succinate and 6 parts by mass of 2,2'-azobis(2,4-dimethyl A mixed solution of valeronitrile) was polymerized for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour, whereby a resin solution (B-2) (solid content concentration: 33% by mass) was obtained. This resin corresponds to (b1) a specific polymer.

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

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

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

Synthesis Example 6 To a flask equipped with a condenser and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was added and replaced with nitrogen. The mixture was heated to 80 ° C, and 100 parts by mass of propylene glycol monomethyl ether acetate, 80 parts by mass of a compound represented by the following formula (Bet-1), and 4 parts by mass of methacrylic acid were added dropwise at this temperature for 1 hour. 2 parts by mass of styrene, 1 part by mass of benzyl methacrylate, 3 parts by mass of 2-hydroxyethyl methacrylate, 4.6 parts by mass of 2-ethylhexyl methacrylate, 2.4 parts by mass N-phenylmaleimide, 3 parts by mass of mono(2-propenyloxyethyl) succinate and 6 parts by mass of 2,2'-azobis(2,4-dimethyl A mixed solution of valeronitrile) was polymerized for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour, whereby a resin solution (B-6) (solid content concentration: 33% by mass) was obtained. This resin corresponds to (b1) a specific polymer.

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

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

[Chemical 4]

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

[Chemical 5]

<Preparation of Colorant Solution> Preparation Example 1 10 parts by mass of the compound (A-1) represented by the following formula was mixed with 90 parts by mass of ethyl lactate to prepare a colorant solution (1).

Production Example 2 to Preparation Example 14 A colorant solution was prepared in the same manner as in Preparation Example 1 except that the compound (A-2) to the compound (A-14) were used instead of the compound (A-1). 2) ~ colorant solution (14). The compound (A-2) to the compound (A-14) are as described later.

A-1: a xanthene compound synthesized in accordance with Synthesis Example 1 of JP-A-2013-190776: a xanthene compound synthesized in accordance with Synthesis Example 3 of JP-A-2013-190776 A-3: a xanthene compound synthesized in accordance with Synthesis Example 2 of JP-A-2013-178478: a xanthene compound synthesized in accordance with Synthesis Example 1 of JP-A-2014-219663 A-5: The cyanine compound (C1-1-1) described in the 27th of the Japanese Patent Publication No. 2015-044982, A-6: Sanfang described in the 20th of the International Publication No. 2012/165537 Methane compound B · A-7: CI solvent blue 45 (antimony compound) · A-8: CI solvent blue 70 (phthalocyanine compound) · A-9: Japanese Patent Laid-Open No. 2015-044982 The azo compound (P1-1) described in the following: A-10: CI Solvent Yellow 114 (quinacridone compound) - A-11: The coumarin compound described in Example 4 of JP-A-4-179955 A-12: exemplified compound III-1 (dipyrromethene compound) described in Formula 54 of Patent No. 5085256. The compound III-7 (squaric acid ruthenium compound) described in Chemical Formula No. 2006-241459, and the formula described in the dye synthesis example 2 of JP-A-2010-211198 ( 2b) Compound represented (salt compound of cationic xanthene chromophore and anionic organometallic complex)

[Chemical 6]

[Chemistry 7]

<Preparation of Pigment Dispersion> Preparation Example 15 15 parts by mass of CI Pigment Blue 15:6 as a coloring agent, and 12.5 parts by mass (solid content concentration: 40% by mass) of BYB as a (b3) dispersing agent (BYK) -LPN21116 (manufactured by BYK Chemie Co., Ltd.) and 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent were processed by a bead mill to prepare a pigment dispersion liquid (a-1).

Preparation Example 16 15 parts by mass of CI Pigment Yellow 138 as a coloring agent, and 12.5 parts by mass (solid content concentration: 40% by mass) of BYK-LPN21116 as a (b3) dispersing agent (BYK) 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent, manufactured by Chemie), and treated by a bead mill to prepare a pigment dispersion (a-2).

Preparation Example 17 15 parts by mass of CI Pigment Red 254 as a coloring agent, and 12.5 parts by mass (solid content concentration: 40% by mass) as a (b3) dispersing agent, BYK-LPN21116 (BYK Chemical (BYK) 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent, manufactured by Chemie), and treated by a bead mill to prepare a pigment dispersion (a-3).

<Preparation and Evaluation of Colored Composition> Example 1 21.3 parts by mass of the pigment dispersion liquid (a-1) and 8.0 parts by mass of the color former solution (1) as the (A) colorant, and (B) resin were used. 6.5 parts by mass (solid content concentration: 33% by mass) of the resin solution (B-2) and 6.0 parts by mass (solid content concentration: 33% by mass) of the resin solution (B-1), and (C) a polymerizable compound 8.2 parts by mass of M-402 (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Toagosei Co., Ltd., and 0.8 parts by mass of 2-benzyl-2-dimethyl group as a photopolymerization initiator Amino-1-(4-morpholinylphenyl)butan-1-one (manufactured by Ciba Specialty Chemicals, Inc., trade name IRGACURE 369) and 0.1 part by mass of NCI -930 (manufactured by ADEKA Co., Ltd.), 0.02 parts by mass of a fluorocarbon surfactant, Megafac F-554 (manufactured by Dianesei Co., Ltd.), and as a solvent Propylene glycol monomethyl ether acetate, prepared to have a solid concentration of 20 % Of the coloring composition (CR1).

Evaluation of heat resistance The colored composition (CR1) was applied onto a soda glass substrate having a SiO ₂ film on which sodium ions were eluted by a spin coater, and then prebaked for 2 minutes using a hot plate at 90 ° C for 2 minutes. A coating film having a film thickness of 2.5 μm was formed. Then, after the substrate was cooled to room temperature, exposure of radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm was performed on the respective coating films at a exposure amount of 400 J/m ² using a high-pressure mercury lamp through a mask. Thereafter, a developing solution containing a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) on the substrates, thereby performing shower development for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further baked in a clean oven at 200 ° C for 30 minutes to form a dot pattern on the substrate. Using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the obtained dot pattern was measured for the chromaticity coordinate value in the International Commission on Illumination (CIE) color system using a C light source and a 2 degree field of view. (x, y) and stimulus value (Y). Then, after the substrate was additionally baked at 230 ° C for 90 minutes, the chromaticity coordinate value (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, the case where the value of ΔE ^* _ab was less than 1.5 was evaluated as "?", the case of 1.5 or more and less than 3.0 was evaluated as "○", and the case of 3.0 or more and less than 5.0 was evaluated as "△", and the case of 5.0 or more was evaluated as "X". The evaluation results are shown in Table 1. Further, the smaller the value of ΔE ^* _ab , the better the heat resistance.

Evaluation of adhesion of the substrate The colored composition (CR1) was applied onto a glass substrate by a spin coater, and after air drying, a coating film having a film thickness of 2.5 μm was formed without prebaking. Then, the substrate is cooled to room temperature, and a high-pressure mercury lamp is used for the coating film on the substrate, and a mask having a dot pattern having a size of 5 μm from 5 μm to 50 μm is interposed, and the illuminance is 17 The exposure amount of mW and 600 J/m ² was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm. Thereafter, a developing solution containing a 0.04% potassium hydroxide aqueous solution at 23 ° C was sprayed onto the coating film on the substrate at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm), thereby performing shower development. Thereafter, the substrates were washed with ultrapure water and air dried. The substrate was observed with an optical microscope. The size (μm) of the minimum dot pattern which was not analyzed by peeling off from the substrate is shown in Table 1. The smaller the size, the better the adhesion.

Evaluation of Coating Film Foreign Matter The colored composition (CR1) was applied onto a glass substrate by a spin coater, and then prebaked by a hot plate at 80 ° C for 10 minutes to form a coating film. Then, after the substrate was cooled to room temperature, radiation of each wavelength of 365 nm, 405 nm, and 436 nm was performed on each of the coating films at an exposure amount of 2,000 J/m ² without using a high-pressure mercury lamp. exposure. Thereafter, a developing solution containing a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) on the substrates, thereby performing shower development for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further 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 an magnification of 50 times using an optical microscope, and the number of confirmed foreign matters in the field of view was counted. This operation was performed at any five places of the cured film for evaluation, and the evaluation was performed based on the following criteria based on the total of the confirmed foreign matters. The results are shown in Table 1.

Evaluation criteria ○: The total amount of foreign matter is less than 5 △: The total amount of foreign matter is 5 or more and less than 50 ×: The total amount of foreign matter is 50 or more

Example 2 to Example 5 A coloring composition (CR2) to a coloring composition were prepared in the same manner as in Example 1 except that the type of the resin solution and the coloring agent solution were changed as shown in Table 1. (CR18). Then, evaluation was performed in the same manner as in Example 1 except that the coloring composition (CR2) to the coloring composition (CR18) were used instead of the coloring composition (CR1). The results are shown in Table 1.

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

Comparative Example 4 21.3 parts by mass of the pigment dispersion liquid (a-1) and 8.0 parts by mass of the color former solution (1) and 10.0 parts by mass of the (B) resin were used as the (A) coloring agent (solid content concentration was 33). (% by mass) of the resin solution (B-1), and 8.2 parts by mass of the (C) polymerizable compound, M-402 (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Toagosei Co., Ltd., 0.8 parts by mass of 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one as a photopolymerization initiator (Ciba Specialty Chemicals) ) Manufactured by the company, IMGACURE 369), 0.1 parts by mass of NCI-930 (made by ADEKA Co., Ltd.), and 0.02 parts by mass of fluoromass surfactant (Megafac) F-554 (manufactured by DiCai Co., Ltd.), 0.825 parts by mass of the compound represented by the above formula (Bet-1), and propylene glycol monomethyl ether acetate as a solvent, and the solid content concentration was 20% by mass of the coloring composition (CR22). Then, evaluation was performed in the same manner as in Example 1 except that the coloring composition (CR22) was used instead of the coloring composition (CR1). The results are shown in Table 1. In the column of the coloring agent (A) and the column of the resin (B) in Table 1, the numerical value in the parentheses is the amount (parts by mass) of each solution.

[Table 1]

no

no

no

Claims (9)

A colored composition comprising (A) a colorant, (B) a resin, and (C) a polymerizable compound, and (B) a resin comprising (b1) a polymer having a cationic site and an anionic site in the same molecule. The colored composition according to claim 1, wherein (b1) the polymer having a cationic portion and an anionic portion in the same molecule comprises a polymerization selected from the group consisting of repeating units represented by the following formula (1) And at least one of a polymer having a repeating unit represented by the following formula (2), In the formula (1), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² and R ¹³ independently of each other represent a divalent organic group, and (C ¹ ) ⁺ represents -N ⁺ R ¹⁴ R ¹⁵ - or -P ⁺ R ¹⁶ R ¹⁷ -, R ¹⁴ to R ¹⁷ independently of each other represent a monovalent organic group, and (A ¹ ) ^- represents CO ₂ ^- , SO ₃ ^- or PO ₄ ^- ; In the formula (2), R ²¹ represents a hydrogen atom or a methyl group, and R ²² and R ²³ each independently represent a divalent organic group, and (A ² ) ^- represents -OP(=O)(-O ^- )O-, - SO ₂ N ^- SO ₂ - or -C(=O)N ^- SO ₂ -, (C ² ) ⁺ represents N ⁺ R ²⁴ R ²⁵ R ²⁶ or P ⁺ R ²⁷ R ²⁸ R ²⁹ , R ²⁴ to R ²⁹ The monovalent organic group is independently represented. The coloring composition according to the second aspect of the invention, wherein the content of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) in the (b1) polymer is 3% by mass to 90%. quality%. The colored composition according to any one of claims 1 to 3, wherein the (A) colorant contains a dye. The coloring composition of claim 4, wherein the dye is selected from the group consisting of xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes. At least one of the groups. A colored hardening film formed by using the coloring composition according to any one of the first to fifth aspects of the invention. A display element comprising the colored cured film as described in claim 6 of the patent application. A solid-state image sensor comprising the colored cured film according to item 6 of the patent application. a polymer having a repeating unit represented by the following formula (1), In the formula (1), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² and R ¹³ independently of each other represent a divalent organic group, and (C ¹ ) ⁺ represents -N ⁺ R ¹⁴ R ¹⁵ - or -P ⁺ R ¹⁶ R ¹⁷ -, R ¹⁴ to R ¹⁷ each independently represent a monovalent organic group, and (A ¹ ) ^- represents CO ₂ ^- , SO ₃ ^- or PO ₄ ^- .