TWI627233B - Colored composition, colored cured film and display element - Google Patents

Abstract

The present invention provides a coloring composition which can form a coloring hardened film which can have both good voltage retention, high contrast, and high heat resistance when a dye is used as a colorant.

The present invention provides a coloring composition comprising a coloring agent containing a compound having a structure represented by the following formula (1), (B) a binder resin, and (C) a polymerizable compound;

[In formula (1), m represents an integer of 0 to 5, R ¹ to R ⁴ independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and R ⁵ represents a monovalent group independently of each other. However, one or more of R ¹ to R ⁴ are a group selected from the following requirements (i) to (v).

(i) is a substituted or unsubstituted unsaturated aliphatic hydrocarbon group, or a substituted or unsubstituted unsaturated alicyclic hydrocarbon group. But not saturated The aliphatic hydrocarbon group may have a linking group selected from -CO-, -COO-, and -CONH- between C-C bonds.

(ii) is an alicyclic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group or an unsaturated alicyclic hydrocarbon group.

(iii) is a substituted or unsubstituted heterocyclic group, or a hydrocarbon group substituted with a heterocyclic group.

(iv) is a hydrocarbon group substituted with at least one selected from the group consisting of -CN, -NO ₂ , -NH ₂ , -SH, and -CONH ₂ .

(v) is a substituted or unsubstituted aliphatic hydrocarbon group having 11 or more carbon atoms. ]

Description

Colored composition, colored cured film and display element

The present invention relates to a coloring composition, a colored hardened film, and a display element. More specifically, the present invention relates to forming a color liquid crystal display element, a solid-state imaging element, an organic EL display element, an electronic paper, and the like for a transmissive or reflective type. A colored composition used for the colored cured film, a colored cured film formed using the colored composition, and a display element including the colored cured film.

When manufacturing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is coated on a substrate and dried, and then a dried coating film is required to be irradiated with radiation. A method of pattern shape (hereinafter referred to as "exposure") and development to obtain pixels of each color (for example, refer to Patent Documents 1 to 2). A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed is also known (for example, refer to Patent Document 3). Furthermore, a method of obtaining pixels of each color by an inkjet method using a pigment-dispersed colored resin composition is also known (for example, refer to Patent Document 4).

In recent years, high contrast of liquid crystal display elements or high definition of solid-state imaging elements have been strongly demanded, and in order to achieve these, some have discussed the application of dyes as colorants. For example, Patent Document 5 proposes to use a specific dibenzopiperan-based dye.

Prior art literature Patent literature

Patent Document 1 Japanese Unexamined Patent Publication No. 2-144502

Patent Document 2 Japanese Unexamined Patent Publication No. 3-52201

Patent Document 3 Japanese Patent Laid-Open No. 6-35188

Patent Document 4 Japanese Patent Laid-Open No. 2000-310706

Patent Document 5 Japanese Patent Laid-Open No. 2010-254964

However, when the dye proposed in Patent Document 5 is used, there is a problem that the contrast of pixels becomes low. On the other hand, when a dye is used, a problem arises in that the voltage retention and heat resistance of various color filters are deteriorated. Therefore, there is a strong need to develop a coloring composition suitable for producing a color filter that has both good voltage retention, high contrast, and high heat resistance.

Therefore, an object of the present invention is to provide a colored composition capable of forming a colored hardened film that has both good voltage retention, high contrast, and high heat resistance when a dye is used as a colorant, and to provide such a colored material. The compound is used as a coloring agent. Another object of the present invention is to provide a color filter including a colored hardened film formed of the coloring composition, and a display element including the color filter.

In view of this fact, the inventors of the present case conducted careful research and found that by using a dye having a specific structure as a colorant, the above problems can be solved, and the present invention has been completed.

That is, the present invention provides a coloring composition comprising (A) a coloring agent containing a compound having a structure represented by the following formula (1) (hereinafter also referred to as "the present colorant"), (B ) Binder resin and (C) polymerizable compound;

[In formula (1), m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of R ⁵ may be the same or different.

R ¹ to R ⁴ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted heterocyclic group. However, the hydrocarbon group may have a bonding group selected from among -CO-, -COO-, and -CONH- between the CC bonds.

R ⁵ independently represents a monovalent base.

However, one or more of R ¹ to R ⁴ are a group selected from the following requirements (i) to (v).

(i) is a substituted or unsubstituted unsaturated aliphatic hydrocarbon group, or a substituted or unsubstituted unsaturated alicyclic hydrocarbon group. However, the unsaturated aliphatic hydrocarbon group may have a linking group selected from among -CO-, -COO-, and -CONH- between C-C bonds.

(ii) is an alicyclic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group or an unsaturated alicyclic hydrocarbon group.

(iii) is a substituted or unsubstituted heterocyclic group, or a hydrocarbon group substituted with a heterocyclic group.

(iv) a hydrocarbon group substituted with at least one selected from the group consisting of -CN, -NO ₂ , -NH ₂ , -SH, and -CONH ₂ (hereinafter also referred to as "substituent group α"). .

(v) is a substituted or unsubstituted aliphatic hydrocarbon group having 11 or more carbon atoms. ]

The present invention also provides a colored cured film formed using the coloring composition and a display element including the colored cured film. Here, the "colored cured film" refers to each color pixel, black matrix, black spacer, and the like used in a display element or a solid-state imaging element.

The present invention also provides a compound having a structure represented by the formula (1).

When the colored composition of the present invention is used, a colored cured film having excellent voltage retention, contrast, and heat resistance can be formed.

Therefore, the coloring composition of the present invention is extremely suitable for the production of solid-state imaging elements such as color liquid crystal display elements, organic EL display elements, display elements such as electronic paper, and CMOS image sensors.

Hereinafter, the present invention will be described in detail.

Coloring composition

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

-(A) Colorant-

The coloring composition of this invention contains this colorant as (A) colorant.

Examples of the hydrocarbon group of R ¹ to R ⁴ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. These hydrocarbon groups may have a bonding group selected from the group consisting of -CO-, -COO-, and -CONH- between the CC bonds.

The aliphatic hydrocarbon group may be saturated or unsaturated, and specific examples thereof include an alkyl group, an alkenyl group, and an alkynyl group. The carbon number of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 24, and particularly preferably 1 to 20. These aliphatic hydrocarbon groups may be linear or branched. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, hexyl, heptyl, and octyl groups. , Nonyl, decyl, undecyl, 1-methyldecyl, dodecyl, 1-methylundecyl, 1-ethyldecyl, tridecyl, tetradecyl, tertiary dodecyl , Pentadecyl, 1-heptyloctyl, hexadecyl, octadecyl, behenyl-1-yl, behenyl-1-yl, behenyl-1-yl, twenty-four Alk-1-yl and the like. Examples of alkenyl include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 1,3-butadienyl, 1-pentenyl, 2 -Pentenyl, 1-hexenyl, 2-ethyl-2-butenyl, 2-octenyl, (4-vinyl) -5-hexenyl, 2-decenyl, and the like. Examples of the alkynyl group include ethyl Alkynyl, 1-propynyl, 1-butynyl, 1-pentynyl, 3-pentynyl, 1-hexynyl, 2-ethyl-2-butynyl, 2-octynyl, (4-ethynyl) -5-hexynyl, 2-decynyl and the like. Examples of the group having a linking group selected from the group consisting of -CO-, -COO-, and -CONH- between the CC bonds of the aliphatic hydrocarbon group include, for example, an ethyl (meth) acrylate group and (formaldehyde) Group) propyl acrylate, (meth) acrylamidoethyl, (meth) acrylamidopropyl and the like.

As the alicyclic hydrocarbon group, an alicyclic hydrocarbon group having 3 to 30 carbon atoms is preferable. The alicyclic hydrocarbon group may be saturated or unsaturated, and specific examples thereof include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a crosslinked cyclic hydrocarbon group, a spiro hydrocarbon group, and a cyclic terpene olefin group. More specifically, cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, tertiary butyl cyclohexyl, cycloheptyl, cyclooctyl, etc .; 1-cyclohexenyl, etc. Cycloalkenyl; tricyclodecyl, decahydro-2-naphthyl, adamantyl, etc. condensed polycyclic hydrocarbon groups; tricyclic [5.2.1.0 ^2,6 ] decane-8-yl, pentacyclopentadecyl , Isofluorenyl, dicyclopentenyl, tricyclopentenyl and other cross-linked cyclic hydrocarbon groups; 1 formed by removing 1 hydrogen atom from spiro [3,4] heptane and spiro [3,4] octane Spiro hydrocarbon groups such as valence groups; cyclic terpene alkenyl groups such as monovalent groups obtained by removing one hydrogen atom from menthol, thujane, long pine needle and the like. Among the aforementioned cycloalkyl and cycloalkenyl groups, a carbon number of 3 to 12 is more preferable.

As the aromatic hydrocarbon group, a carbon number of 6 to 20 is preferable, and a carbon number of 6 to 10 is more preferable. Specific examples of the aromatic hydrocarbon group include an aryl group. Herein, the "aryl group" in the present invention means a monocyclic to tricyclic aromatic hydrocarbon group, and specifically, phenyl, benzyl, o-tolyl, m-tolyl, p-tolyl, Xylyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, 9-fluorenyl and the like.

The heterocyclic group of R ¹ to R ⁴ is not particularly limited as long as it is a monovalent heterocyclic ring, but is preferably a monocyclic or condensed bicyclic heterocyclic group having 3 to 10 membered rings. Examples include ethylene oxide, propylene oxide, pyrrolidinyl, imidazolyl, pyrazolidyl, Phosphono, thio Thiomorpholinyl, piperidinyl, N-hexahydropyridyl, piperidinyl Base Alicyclic heterocyclic groups such as homopiperazinyl, 1,3-dioxolane-2-yl, pyridyl, pyridine Base, pyrimidinyl, , Quinolinyl, isoquinolinyl, fluorene base, Pyridyl, quinine Phosphono, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, benzothiazolyl, Aromatic heterocyclic groups such as oxazolyl, indolyl, indazolyl, benzimidazolyl, phthalimide, thienyl, furyl, piperanyl, and purinyl.

Among them, R ¹ to R ^{4 are} preferably a hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably R ¹ to R ⁴ are all aromatic hydrocarbon groups, R ¹ and R ⁴ are aromatic hydrocarbon groups, and R ² and R ³ are aliphatic. Hydrocarbyl appearance.

R ⁵ is a monovalent, if it is not particularly limited, but is preferably a monovalent group containing a hetero atom, for example, include _{^{-CO 2 -, -CO 2 H,}} -CO 2 M, -CO 2 R 6 _{^{, -SO 3 -, -SO 3 H}} , -SO 3 M, -SO 3 R 7, -SO 2 NHR 8, -SO 2 NR 9 R 10, -SO 2 -ON = CR 11 R 12, -SO 2 NHNHR ¹³ , -SO ₂ SR ¹⁴ , -SO ₂ NHSO ₂ R ¹⁵ . Here, R ⁶ to R ¹¹ and R ¹³ to R ¹⁵ each independently represent a substituted or unsubstituted hydrocarbon group, R ¹² represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon group, and M represents a sodium atom or a potassium atom. .

As the hydrocarbon groups of R ⁶ to R ¹¹ and R ¹³ to R ¹⁴ , aliphatic hydrocarbon groups and aromatic hydrocarbon groups are preferred, and alkyl groups having 1 to 30 carbon atoms and aryl groups having 6 to 30 carbon atoms are more preferred. The carbon number of the alkyl group is preferably 1 to 24, and more preferably 1 to 18. The carbon number of the aryl group is preferably 6-20, and more preferably 6-10.

R ^{12 is} preferably an aliphatic hydrocarbon group, more preferably an alkyl group having 1 to 24 carbon atoms, and particularly preferably an alkyl group having 1 to 12 carbon atoms.

R ^{15 is} preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, more preferably an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 10 carbon atoms.

Specific examples of the hydrocarbon group include the same as those described above.

The hydrocarbon groups of R ¹ to R ⁴ and R ⁶ to R ¹⁵ and the heterocyclic groups of R ¹ to R ⁴ may further have a substituent within a range not exceeding the gist of the present invention. The position and number of the substituents are arbitrary, and when there are two or more substituents, the substituents may be the same or different. Examples of such a substituent include a halogen atom, a hydroxyl group, a cyano group, a methylamino group, a carboxyl group, a nitro group, an amine group, a thiol group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and N Substituted amine, amido, alkylcarbonyl, alkoxycarbonyl, alkanesulfonyl, alkylaminosulfonyl, trialkylsilyl, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, heterocyclic group, etc. . These substituents may further have a substituent.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, hexyloxy, 2-ethylhexyloxy, octyloxy, dodecyloxy, and tertiary dodecyl C _1-12 alkoxy such as alkoxy. Examples of the aryloxy group include a phenoxy group and a benzyloxy group.

Examples of the alkylthio group include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, pentylthio, isopentylthio, neopentylthio, and cyclopentyl. Thio, hexylthio, cyclohexylthio, heptylthio, cycloheptylthio, octylthio, 2-ethylhexylthio, cyclooctylthio, nonylthio, decylthio, tricyclodecylthio Methyl, methoxypropylthio, ethoxypropylthio, hexyloxypropylthio, 2-ethylhexyloxypropylthio, methoxyhexylthio, undecylthio, dodecylthio C _1-20 alkylthio, including tetradecylthio, tertiary dodecylthio, hexadecylthio, octadecylthio, and the like. Examples of the arylthio group include a phenylthio group and the like.

Examples of the substituent of the N-substituted amine group include a C _1-6 alkyl group and a C _6-10 aryl group. Specific examples include the same ones as described above.

Examples of the alkylcarbonyl group include a C _1-6 alkylcarbonyl group such as a methylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, and a butcarbonyl group.

Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, 2-ethylhexyloxycarbonyl, dodecylcarbonyl, and octadecyl C _1-20 alkoxycarbonyl such as alkylcarbonyl.

Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a hexanesulfonyl group, a decylsulfonyl group, an undecylsulfonyl group, a dodecylsulfonyl group, and a tetradecylsulfonyl group. C _1-20 alkylsulfonyl, such as triphenyl, tertiary dodecanesulfonyl, hexadecylsulfonyl, octadecylsulfonyl and the like.

Examples of the alkylaminesulfonyl group include methylaminesulfonyl, ethylaminesulfonyl, dimethylaminesulfonyl, propylaminesulfonyl, isopropylaminesulfonyl, and butyl Aminosulfonyl, hexylaminesulfonyl, octylaminesulfonyl, 2-ethylhexylaminesulfonyl, undecylaminesulfonyl, dodecylaminesulfonyl, 1-heptyl C _1-20 alkylaminesulfonyl groups such as octylaminesulfonyl.

Examples of the trialkylsilyl group include triC _1-6 alkylsilyl groups such as trimethylsilyl group.

Specific examples of the aliphatic hydrocarbon group, the aromatic hydrocarbon group, and the heterocyclic group include the same ones as described above.

m is an integer of 0 to 5, but is preferably 0 to 3, and more preferably 1 or 2.

In addition, one or more of R ¹ to R ⁴ in formula (1) need to be a group selected from the following requirements (i) to (v).

(i) is a substituted or unsubstituted unsaturated aliphatic hydrocarbon group, or a substituted or unsubstituted unsaturated alicyclic hydrocarbon group. However, the unsaturated aliphatic hydrocarbon group may have a linking group selected from among -CO-, -COO-, and -CONH- between C-C bonds.

(ii) is an alicyclic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group or an unsaturated alicyclic hydrocarbon group.

(iii) is a substituted or unsubstituted heterocyclic group, or a hydrocarbon group substituted with a heterocyclic group.

(iv) is a hydrocarbon group substituted with at least one selected from the substituent group α.

(v) is a substituted or unsubstituted aliphatic hydrocarbon group having 11 or more carbon atoms.

Examples of the unsaturated aliphatic hydrocarbon group in the requirements (i) and (ii) include the same ones as described above, but an alkenyl group is preferred among them. Its carbon number is preferably 2 to 20, more preferably 2 to 10, and particularly preferably 2 to 6.

Examples of the unsaturated alicyclic hydrocarbon group of the requirements (i) and (ii) include the same ones as described above, and among them, a cycloalkenyl group is preferred. Its carbon number is preferably 4 to 8, more preferably 5 or 6.

Examples of the heterocyclic group in the requirement (iii) include the same ones as described above, but an alicyclic heterocyclic group is preferred. The hydrocarbon group of the requirement (iv) is preferably a saturated hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group. The carbon number of the saturated aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 2 to 6.

The substituent group α of the requirement (iv) is more preferably -CN or -NO ₂ . Moreover, as a hydrocarbon group of the requirement (iv), an aliphatic hydrocarbon group and an aromatic hydrocarbon group are preferable. The carbon number of the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 2 to 6.

Element (v) The aliphatic hydrocarbon group having 11 or more carbon atoms may be saturated or unsaturated. Specific examples include a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group having a carbon number of 11 or more in the same ones as described above. The carbon number of the aliphatic hydrocarbon group is preferably 11-20, and more preferably 11-16. Examples of the substituent of the requirement (v) include a halogen atom, a hydroxyl group, a cyano group, a methyl group, a carboxyl group, a nitro group, an amine group, a thiol group, an alkoxy group, an aryloxy group, an alkylthio group, and an aromatic sulfur Group, N-substituted amino group, alkylcarbonyl group, alkoxycarbonyl group, alkanesulfonyl group, alkylaminesulfonyl group, trialkylsilyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group and the like. Specific examples of the substituent include the same as those described above.

Among the requirements (i) to (v), one or more of R ¹ to R ⁴ are preferably a substituted or unsubstituted unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group, A hydrocarbon group substituted with a heterocyclic group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group substituted with at least one selected from the substituent group α, a substituted or unsubstituted aliphatic hydrocarbon group having a carbon number of 11 or more, more preferably A substituted or unsubstituted unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group substituted with at least one selected from the substituent group α.

As a structure shown by Formula (1), the following structures are mentioned, for example. Among them, the structural formulae (a1), (a10), (a16), (a17), (a19), (a20), (a22), (a39) to (a45) are preferable. However, R ^a represents 2-ethylhexyl.

When the structure represented by the formula (1) is cationic, the compound having the structure represented by the formula (1) becomes electrically neutral and has an anion. Examples of the anion include a halogen ion, a boron anion, a phosphate anion, a carboxylic acid anion, a sulfuric acid anion, an organic sulfonic acid anion, a nitrogen anion, and a methyl metal compound anion. More specifically, for example, an anion described in Japanese Patent Application Publication No. 2007-503477 is mentioned.

When the structure represented by the formula (1) is anionic, the compound having the structure represented by the formula (1) becomes electrically neutral and has a cation. Examples of the cation include a metal cation and an onium cation. Examples of the metal cation include monovalent metal cations such as lithium ions, sodium ions, and potassium ions, and divalent metal cations such as magnesium ions and calcium ions. Examples of onium cations include ammonium cations and sulfonium cations. Examples of the ammonium cation include tetramethylammonium, tetraethylammonium, monostearyltrimethylammonium, distearyldimethylammonium, tristearylmonomethylammonium, and cetyl Trimethylammonium, trioctylmethylammonium, dioctyldimethylammonium, monolauryltrimethylammonium, dilauryldimethylammonium, trilaurylmethylammonium, tripentylbenzylammonium , Trihexyl benzyl ammonium, trioctyl benzyl ammonium, trilauryl benzyl ammonium, benzyl dimethyl stearyl ammonium, benzyl dimethyl octyl ammonium, dialkyl (alkane The group is C14 ~ C18) dimethyl ammonium and the like. Examples of the phosphonium cation include tetraoxane such as methyltrioctylfluorene, octyltributylphosphonium, dodecyltributylphosphonium, hexadecyltributylphosphonium, dihexyldioctylphosphonium and the like Aryl trialkyl fluorene such as benzamidine, benzyl tributyl fluorene, dialkyl diaryl fluorene such as dibutyl diphenyl fluorene, alkyl triphenyl fluorene such as butyl triphenyl fluorene , Benzyltriphenylphosphonium, etc. tetraarylphosphonium and the like.

This colorant can be manufactured by a suitable method, For example, the method similar to the Example of Unexamined-Japanese-Patent No. 2010-254964 and the Example 3 of Unexamined-Japanese-Patent No. 2013-011869 are mentioned. The colorant obtained as described above is soluble in various organic solvents such as ketones such as cyclohexanone, and has excellent heat resistance.

In the present invention, the colorant can be used alone or in combination of two or more.

The coloring composition of the present invention contains the present colorant as a colorant, and may further include other colorants. Other colorants are not particularly limited, and colors and materials can be appropriately selected according to the application.

As other coloring agents, any pigments, dyes other than this colorant, and natural pigments can be used, but in the sense of obtaining pixels with high brightness and color purity, organic pigments and organic dyes are preferred, and organic pigments are particularly preferred. pigment.

Examples of the organic pigment include compounds classified as pigments in the color index (C.I .; issued by The Society of Dyers and Colourists), that is, those having a color index (C.I.) number as described below.

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 Green 7, CI Pigment Green 36, CI Pigment Green 58; CI Pigment Blue 15: 6. CI Pigment Blue 16, CI Pigment Blue 80; 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; CI Pigment Orange 38; CI Pigment Purple 23.

Other examples include those disclosed in Japanese Patent Laid-Open No. 2001-081348, Japanese Patent Laid-Open No. 2010-026334, Japanese Patent Laid-Open No. 2010-237384, Japanese Patent Laid-Open No. 2010-237569, and Japanese Patent Laid-Open No. Lake pigments such as 2011-006602 and Japanese Patent Application Laid-Open No. 2011-145346.

Further, as the dye, a triarylmethane-based dye, an anthraquinone-based dye, an azo-based dye, and the like are preferable. More specific examples include Japanese Patent Application Publication No. 10/123071, Japanese Patent Application Publication No. 2011-116803, Japanese Patent Application Publication No. 2011-117995, Japanese Patent Application Publication No. 2011-133844, and Japanese Patent Application Publication No. 2011. -174987, and other organic dyes.

The coloring composition of the present invention is preferably used for the formation of blue pixels. In this case, it is preferable to include the present colorant as the (A) colorant and at least one selected from the group containing a blue pigment, a blue dye, a purple pigment, and a purple dye as another colorant. In this case, the content ratio of the colorant in the total colorant is preferably 0.1 to 80% by mass, preferably 1 to 80% by mass, more preferably 5 to 60% by mass, and particularly preferably 10 to 40% by mass.

In the present invention, other pigments that are arbitrarily mixed may be purified by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination thereof. In addition, these pigments may be used by modifying the surface of the particles with a resin as necessary. Examples of the resin in which the particle surface of the pigment is modified include a carrier resin described in Japanese Patent Application Laid-Open No. 2001-108817, and various commercially available resins for pigment dispersion. As a method for coating the carbon black surface, for example, methods described in Japanese Patent Application Laid-Open No. 9-71733, Japanese Patent Application Laid-Open No. 9-95625, and Japanese Patent Application Laid-Open No. 9-124969 can be used. In addition, organic pigments can also use so-called The salt mill is used to refine the primary particles. As a method for salt milling, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be adopted.

In addition, in the present invention, other coloring agents are optionally mixed, and may further contain a well-known dispersant and a dispersing aid. Examples of well-known dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ester-based dispersants, polyoxyethylene alkylphenyl ether-based dispersants, and polydisperses. A glycol diester-based dispersant, a sorbitan fatty acid ester-based dispersant, a polyester-based dispersant, an acrylic-based dispersant, and the like, and examples of the dispersion aid include pigment derivatives.

The aforementioned dispersants can be obtained commercially. For example, as the acrylic dispersant, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (the above are manufactured by BYK), etc. Examples of the urethane-based dispersant include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK), Solsperse 76500 (Lubrizol (shares) ), Etc .; Examples of the polyethyleneimine-based dispersant include Solsperse 24000 (manufactured by Lubrizol Co., Ltd.); and examples of the polyester-based dispersant include Ajisper PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881 (the above is made by Ajinomoto Fine-Techno (stock) company) and the like.

Moreover, as said pigment derivative, a copper cyanine cyanine, a diketopyrrolopyrrole, a sulfonic acid derivative of a quinophthalone, etc. are mentioned.

In the present invention, other coloring agents can be used alone or in combination of two or more.

When other colorants are contained, the content of the other colorants is preferably 99.9% by mass or less, more preferably 99% by mass or less, more preferably 95% by mass or less, and particularly preferably 90% by mass relative to the total content of the colorant. %the following. The lower limit value is not particularly limited as long as it is 0.01% by mass or more.

From the viewpoint of forming a heat-resistant, high-brightness pixel with excellent color purity, or a black matrix and black spacer with excellent light-shielding properties, the content ratio of the (A) colorant is usually the solid content of the coloring composition. Medium is 5 to 70 mass%, preferably 5 to 60 mass%, and more preferably 10 to 40 mass%. The solid content here is a component other than the solvent mentioned later.

-(B) Binder resin-

The (B) binder resin of the present invention is not particularly limited, but a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group is preferred. Among them, a polymer having a carboxyl group (hereinafter also referred to as a “carboxyl-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as “unsaturated Saturated monomer (b1) ".) And a copolymerizable other copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as" unsaturated monomer (b2) ").

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloxyethyl], and ω-carboxyl. Polycaprolactone mono (meth) acrylate, p-vinylbenzoic acid and the like.

These unsaturated monomers (b1) can be used alone or in combination of two or more.

Examples of the unsaturated monomer (b2) include, for example, N-substituted maleimide of N-phenylmaleimide and N-cyclohexylmaleimide; for example, benzene Aromatic vinyl compounds of ethylene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl epoxypropyl ether, and pinene; such as (meth) acrylic acid Methyl ester, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, (meth) Benzyl acrylate, polyethylene glycol (polymerization degree 2-10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2-10) methyl ether (meth) acrylate, polyethylene glycol ( Degree of polymerization 2 ~ 10) Mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 ~ 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isoamyl (meth) acrylate, ( (5.2.1.0 ^2,6 ) decyl-8-methacrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, (meth) acrylic acid-4- Hydroxyphenyl esters, ethylene oxide denatured (meth) acrylates of p-propofol, (meth) acrylic acid Glycidyl acid, -3,4-epoxycyclohexyl methyl (meth) acrylate, 3-[(meth) acryloxymethyl] oxycyclobutane, 3-[(meth) propylene (Meth) acrylate of ethoxymethyl] -3-ethyloxycyclobutane; such as cyclohexyl vinyl ether, isofluorenyl vinyl ether, tricyclic [5.2.1.0 ^2,6 ] decane- 8-based vinyl ether, pentacyclopentadecyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxycyclobutane vinyl ether; such as polystyrene, poly (meth) acrylic acid Macromonomers such as methyl esters, poly (n-butyl) methacrylate, and polysiloxanes having a mono (meth) acrylfluorene group at the end of the polymer molecular chain.

These unsaturated monomers (b2) can be used alone or in combination of two or more.

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) within the aforementioned range, a colored composition having excellent alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, Japanese Unexamined Patent Publication No. 7-140654, Japanese Unexamined Patent Publication No. 8-259876, and Japan Japanese Patent Laid-Open No. 10-31308, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open No. 2004-101728 Copolymers of No. 1 and others.

In the present invention, for example, Japanese Patent Laid-Open No. 5-19467, Japanese Patent Laid-Open No. 6-230212, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 9-325494, and Japanese Patent Laid-Open No. 11 As disclosed in -140144, Japanese Patent Application Laid-Open No. 2008-181095, and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylfluorenyl group in a side chain may be used as a binder resin.

The polystyrene of the binder resin of the present invention is determined by colloidal permeation chromatography (hereinafter referred to as GPC) (dissolution solvent: tetrahydrofuran). The calculated weight average molecular weight (Mw) is usually 1,000 to 100,000, preferably 3,000 to 50,000. By being in the state as described above, the residual film rate, pattern shape, heat resistance, electrical characteristics, and resolution of the film can be further improved, and the occurrence of dry foreign matter during coating can be suppressed at a high level.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin of the present invention is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0. The Mn referred to herein is a polystyrene-equivalent number average molecular weight measured by GPC (dissolution solvent: tetrahydrofuran).

The binder resin of the present invention can be produced by a known method. For example, the binder resin disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, and International Publication No. 07/029871 can be used. Method to control its structure or Mw, Mw / Mn.

In this invention, a binder resin can be used individually or in mixture of 2 or more types.

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, and more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the colorant (A). By being in such a state as described above, the alkali developability, the storage stability of the coloring composition, and the chromaticity characteristics can be further improved.

-(C) polymerizable compound-

In the present invention, the polymerizable compound refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an ethylene oxide group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, as the polymerizable compound, A compound having two or more (meth) acrylfluorenyl groups or a compound having two or more N-alkoxymethylamino groups is preferable.

Specific examples of the compound having two or more (meth) acrylfluorenyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, and caprolactone. Ester-denatured polyfunctional (meth) acrylates, alkylene oxide-denatured polyfunctional (meth) acrylates, and polyfunctional aminomethyl esters obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate Acid ester (meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride, and the like.

Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; glycerol, trimethylolpropane, and the like. Trivalent or higher aliphatic polyhydroxy compounds of pentaerythritol and dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, and pentaerythritol tri (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, glycerol dimethacrylate, and the like. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and the like. Examples of the acid anhydride include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides of hexahydrophthalic anhydride, pyromellitic anhydride, and Tetracarboxylic dianhydride of pyromellitic dianhydride and benzophenone tetracarboxylic dianhydride.

Examples of the polyfunctional (meth) acrylate modified with caprolactone include compounds described in paragraphs [0015] to [0018] of Japanese Patent Application Laid-Open No. 11-44955. Examples of the alkylene oxide-denatured polyfunctional (meth) acrylate include bisphenol A di (meth) acrylate modified with at least one selected from the group consisting of ethylene oxide and propylene oxide, Denaturation using at least one kind selected from ethylene oxide and propylene oxide and tri (meth) acrylate isotricyanate, and denaturation using at least one kind selected from ethylene oxide and propylene oxide Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate denatured with at least one selected from ethylene oxide and propylene oxide, using ethylene oxide selected from And pentaerythritol tetra (meth) acrylate denatured with at least one kind of propylene oxide, and dipentaerythritol penta (meth) acrylate denatured with at least one kind selected from ethylene oxide and propylene oxide, using Dipentaerythritol hexa (meth) acrylate and the like selected from at least one selected from ethylene oxide and propylene oxide.

Examples of the compound having two or more N-alkoxymethylamine groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. In addition, the melamine structure and the benzoguanamine structure refer to those having one or more Cyclic or triphenyl substituted The chemical structure of a ring as a basic skeleton is a concept that also includes melamine, benzoguanamine, or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ', N', N ", N" -hexa (alkoxymethyl) melamine, N, N, N ', N'-tetrakis (alkoxymethyl) benzoguanamine, N, N, N', N'-tetrakis (alkoxymethyl) acetylene urea and the like.

Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, and polyfunctional (meth) modified with caprolactone Acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate with carboxyl group, N, N, N ', N', N ", N" -hexa (alkoxy) Methyl) melamine, N, N, N ', N'-tetrakis (alkoxymethyl) benzoguanamine are preferred. From the viewpoint that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and dross and film residue are hardly generated on the substrate and the light-shielding layer of the unexposed portion, the trivalent or higher aliphatic polyhydroxy compound and Among the polyfunctional (meth) acrylates obtained by the (meth) acrylic acid reaction, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferred. Among polyfunctional (meth) acrylates having a carboxyl group, compounds obtained by reacting pentaerythritol triacrylate with succinic anhydride and compounds obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride are particularly preferred.

In the present invention, the (C) polymerizable compound may be used alone or in combination of two or more.

The content of the (C) polymerizable compound of the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 700 parts by mass, and particularly preferably 30 to 500 parts by mass, based on 100 parts by mass of the colorant (A). It is preferably 50 to 150 parts by mass. By being in the state as described above, it is possible to further improve the hardenability and alkali developability, and to suppress the occurrence of dross and film residue on the substrate or the light-shielding layer of the unexposed portion at a high level.

-Photopolymerization initiator-

The coloring composition of the present invention may contain a photopolymerization initiator. According to the foregoing, the coloring composition can be given radiation sensitivity. The photopolymerization initiator used in the present invention is a compound that generates active species that can initiate polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet rays, extreme ultraviolet rays, electron beams, and X-rays.

Examples of the photopolymerization initiator include thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, Based compounds, O-fluorenyl oxime based compounds, onium salt based compounds, benzoin based compounds, benzophenone based compounds, α-diketone based compounds, polynuclear quinone based compounds, diazonium based compounds, pyrimidine Ester-based compounds and the like.

In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is selected from the group consisting of thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, At least one of the group of the compound and the O-fluorenyl oxime compound is preferable.

Among the preferred photopolymerization initiators of the present invention, as specific examples of the thioxanthone-based compound, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropyl Thiothioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4- Diisopropylthioxanthone and the like.

Further, as a specific example of the acetophenone-based compound, 2-methyl-1- [4- (methylthio) phenyl] -2-N- Phenylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-N- Phenylphenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-N- Phenylphenyl) butan-1-one and the like.

Moreover, as a specific example of the said biimidazole-based compound, 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.

When a biimidazole-based compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor in combination from the viewpoint of improving sensitivity. The "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole-based compound by exposure. Examples of the hydrogen donor include 2-thiol benzothiazole and 2-thiol benzo. Thiol-based hydrogen donors such as azole, amine-based hydrogen donors such as 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, etc. . In the present invention, hydrogen donors can be used alone or in combination of two or more. From the viewpoint of further improving sensitivity, one or more thiol-based hydrogen donors and one or more amine-based hydrogen donors can be combined. It is ideal for practical use.

Also, as the aforementioned three Specific examples of the compounds are 2,4,6-ginseno (trichloromethyl) -s-tri , 2-methyl-4,6-bis (trichloromethyl) -s-tri , 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -s-tri , 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -s-tri , 2- [2- (4-Diethylamino-2-methylphenyl) vinyl] -4,6-bis (trichloromethyl) -s-tri , 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -s-tri , 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-tri , 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-tri , 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-tri Halomethyl Department of compounds.

Further, as specific examples of the O-fluorenyl oxime compound, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzylidene) Oxime), ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamidooxime), ethyl Ketone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofurylmethoxybenzyl) -9H-carbazol-3-yl]-, 1- (O-ethylfluorenyl Oxime), ethyl ketone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolyl) methoxybenzidine Group} -9H-carbazol-3-yl]-, 1- (O-ethylamidoxime) and the like. As commercially available O-fluorenyl oxime-based compounds, NCI-831, NCI-930 (the above are manufactured by ADEKA Corporation), DFI-020, DFI-091 (the above are manufactured by DAITO CHEMIX Co., Ltd.) )Wait.

In the present invention, when a photopolymerization initiator other than a biimidazole-based compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. Examples of the aforementioned sensitizer include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-di Ethylaminoacetophenone, 4-dimethylaminophenylacetone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4 -Diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzyl) coumarin, 4- (diethylamino) chalcone Wait.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, and particularly preferably 10 to 60 parts by mass relative to 100 parts by mass of the polymerizable compound. . By setting it as such, hardenability and film characteristics can be further improved.

-Solvent-

The coloring composition of the present invention is one containing the aforementioned components (A) to (C) and other components optionally added, but is usually prepared by mixing a solvent as a liquid composition.

As the aforementioned solvent, as long as it disperses or dissolves the components (A) to (C) or other components constituting the coloring composition, does not react with these components, and has moderate volatility, it can be appropriately selected and used. .

Examples of the aforementioned solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol. Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether 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, (Poly) olefin-based glycol monoalkyl esters such as dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; alkyl lactates such as methyl lactate and ethyl lactate; methanol (Cyclo) alkanols such as ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethylhexanol, cyclohexanol; ketones such as diacetone alcohol Alcohols; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol Monomethyl ether Esters, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxy butyl acetate -3- (Poly) olefin glycol monoalkyl ether acetates such as methyl-3-methoxybutyl ester; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol di Ethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; propylene glycol diacetate, 1,3-butanediol diacetate, Diacetates such as 1,6-hexanediol diacetate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Alkoxycarboxylic acid esters such as ethyl ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl propionate; ethyl acetate, n-propyl acetate, acetic acid Isopropyl ester, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyrate Butyl ester, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2-oxobutyrate, and other esters; toluene, xylene And other aromatic hydrocarbons; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyridine Pyridoxines such as pyridone or lactams.

Among these solvents, from the viewpoints of solubility, pigment dispersibility, coatability, etc., (poly) olefin-based glycol monoalkyl ethers, alkyl lactates, and (poly) olefin-based glycol monoalkanes Ether ether acetates, other ethers, ketones, diacetates, alkoxycarboxylic esters, and other esters are preferred, especially propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethyl acetate. Glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol Dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diethyl Acid esters, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxypropionate Butyl, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate Waiting is ideal.

In this invention, a solvent can be used individually or in mixture of 2 or more types. When used in combination, it is preferred that at least (poly) olefin-based glycol monoalkyl ethers and (poly) olefin-based glycol monoalkyl ether acetates and (poly) olefin-based glycol monoalkyl ether acetate be used. Esters are used in combination with alkoxycarboxylic acid esters.

The content of the solvent is not particularly limited, but an amount in which the total concentration of each component of the solvent excluding the coloring composition is 5 to 50% by mass is preferable, and an amount of 10 to 40% by mass is more preferable. By setting it as such, the coloring agent dispersion liquid with favorable dispersibility and stability, and the coloring composition with favorable coating property and stability can be obtained.

-additive-

The coloring composition of the present invention may contain various additives if necessary.

Examples of the additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); interfaces of fluorine-based surfactants and silicon-based surfactants; Active agent: vinyltrimethoxysilane, vinyltriethoxysilane, vinyl ginseng (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyl Second Oxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropane Adhesion promoters such as trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc .; 2,2-thiobis (4-methyl -6-Third-Butylphenol), 2,6-Di-Third-Butylphenol, Pentaerythritol [3- (3,5-Di-Third-Butyl-4-hydroxyphenyl) propionate], 3, 9-bis [2- [3- (3-Third-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4, 8,10-tetraoxa-spiro [5.5] undecane, thiodivinylbis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], etc. Antioxidants; anti-agglomerating agents such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol , 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, etc. Slag improving agent; succinic acid mono [2- (meth) acryloxyethyl], phthalic acid mono [2- (meth) acryloxyethyl], ω-carboxy polycaprolactone mono (Meth) acrylic acid esters, such as developability improvers. In addition, in the present invention, it is not always necessary to include an ultraviolet absorber such as benzotriazole, benzophenone, benzoate, cyanoacrylate, and the like.

The colored composition of the present invention can be prepared by an appropriate method. Examples of the preparation method include methods disclosed in Japanese Patent Application Laid-Open No. 2008-58642 and Japanese Patent Application Laid-Open No. 2010-132874. When both the dye and the pigment are used as the colorant, as disclosed in Japanese Patent Application Laid-Open No. 2010-132874, a dye solution that passes the first filter after passing the dye solution through the first filter may be used. A method of mixing with a separately prepared pigment dispersion and the like, and passing the obtained colored composition through a second filter. It is also possible to dissolve the dye with the aforementioned components (B) to (C) and other components used as necessary in a solvent, so that the obtained solution passes through the first filter, and the solution passing through the first filter and A method of preparing a pigment dispersion liquid prepared separately by mixing the obtained colored composition with a second filter. Alternatively, after passing the dye solution through the first filter, the dye solution passing through the first filter may be mixed and dissolved with the components (B) to (C) and other components used as necessary, so that the obtained solution passes through. A method of preparing a second filter by mixing a solution that has passed through the second filter with a separately prepared pigment dispersion so that the obtained colored composition passes through the third filter.

Colored hardened film and manufacturing method thereof

The coloring cured film of the present invention is formed by using the coloring composition of the present invention, and specifically means each color pixel, a black matrix, a black spacer, and the like used in a color filter.

Hereinafter, a colored hardened film used for a color filter and a method for forming the same will be described.

As a method of manufacturing a color filter, the following method is mentioned first. First, a light-shielding layer (black matrix) is formed on a surface of a substrate as necessary to partition a pixel-forming portion. Next, on this substrate, for example, after the red liquid color composition of the radiation-sensitive coloring composition of the present invention is applied, pre-baking is performed and the solvent is evaporated to form a coating film. Next, after this coating film is exposed through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is melt | dissolved and removed. After that, by performing post-baking, the shape A pixel array in which a red pixel pattern (colored hardened film) is arranged in a certain arrangement.

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

The black matrix can be formed by forming a metal thin film such as chromium by sputtering or vapor deposition into a desired pattern by a photolithography method. However, a radiation-sensitive coloring composition in which a black pigment is dispersed may be used. The object is formed in the same manner as in the case of forming the pixels.

Examples of the substrate used when forming a color filter include glass, silicon, polycarbonate, polyester, aromatic polyimide, polyimide, polyimide, and the like.

In addition, appropriate pretreatments such as chemical treatment using a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction method, and vacuum evaporation may be performed on such substrates in advance as necessary. .

When applying the radiation-sensitive coloring composition to a substrate, a suitable method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slot die coating method (slit coating method), or a rod coating method can be used. The coating method is particularly preferably a spin coating method or a slot die coating method.

Pre-baking is usually performed by combining reduced pressure drying and heat drying. Drying under reduced pressure is usually carried out until 50 to 200 Pa. The conditions for heating and drying are usually about 1 to 10 minutes at 70 to 110 ° C.

The coating thickness, as the film thickness after drying, is usually 0.6 to 8 μm, and preferably 1.2 to 5 μm.

Examples of a light source for radiation used when forming at least one selected from a pixel and a black matrix include a xenon lamp, a halogen lamp, a tungsten filament lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, and a medium-voltage lamp. Mercury lamp, low-pressure mercury lamp and other lamp light sources or argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser and other laser light sources. As an exposure light source, an ultraviolet LED can also be used. The wavelength is preferably radiation in the range of 190 to 450 nm.

Generally speaking, the radiation exposure is preferably 10 to 10,000 J / m ² .

As the alkaline developer, for example, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] Aqueous solutions such as -7-undecane, 1,5-diazabicyclo- [4.3.0] -5-nonene are preferred.

To the alkali developing solution, for example, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, or a surfactant may be added. Furthermore, after alkali development, it is usually washed with water.

As the development processing method, a shower development method, a spray development method, a dip development method, a immersion (container) development method, and the like can be applied. The developing conditions are preferably 5 to 300 seconds at room temperature.

Post-baking conditions are usually about 10 to 60 minutes at 180 to 280 ° C.

The film thickness of the pixels formed as described above is usually 0.5 to 5 μm, and preferably 1.0 to 3 μm.

As a second method for manufacturing a color filter, it is disclosed in Japanese Patent Application Laid-Open No. 7-318723, Japanese Patent Application Laid-Open No. 2000-310706, and the like, and a method of obtaining pixels of each color by an inkjet method can be adopted. In this method, first, a partition wall also having a light shielding function is formed on the surface of the substrate. Next, in the formed partition wall, for example, the liquid composition of the blue thermosetting coloring composition of the present invention is ejected by an inkjet device, and then the pre-baking is performed to evaporate the solvent. Next, after exposing the coating film as necessary, it is cured by post-baking to form a blue pixel pattern.

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

In addition, the partition wall not only has a light-shielding function, but also exhibits a function that the thermosetting coloring composition of each color discharged from the partition does not mix colors. Therefore, 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-sensitive composition.

The substrate or the radiation source used when forming the color filter, or the method or conditions for pre-baking or post-baking are the same as the first method described above. As described above, the film thickness of the pixels formed by the inkjet method is about the same as the height of the partition wall.

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

The coloring composition of the present invention can also be suitably used in the formation of any colored cured film of each color pixel, black matrix, black spacer, etc. used in the color filter.

The color filter including the colored hardened film of the present invention formed as described above has extremely high brightness and high coloring power. Therefore, it is suitable for color liquid crystal display elements, color image pickup tube elements, color detectors, organic EL display elements, and electronic paper. Etc. are extremely useful. It is to be noted that a display element described later may include at least one coloring cured film formed using the coloring composition of the present invention.

Display element

The display element of this invention is a person provided with the colored hardened film of this invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

The color liquid crystal display element provided with the colored hardened film of the present invention may be a transmissive type or a reflective type, and an appropriate structure may be adopted. 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 driving substrate and the substrate on which the color filter is formed are opposed to each other through a liquid crystal layer. Structure; even Adopted: a substrate on which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is arranged and an ITO (tin-doped indium oxide) electrode or IZO (a mixture of indium acid and zinc oxide) The substrate of the electrode has a structure opposed to each other through the liquid crystal layer. The latter structure has the advantages that the aperture ratio can be significantly improved, and a bright and high-definition liquid crystal display element can be obtained. In the latter configuration, a black matrix or a black spacer may be formed on either of the substrate side on which the color filter is formed and the substrate side on which the ITO electrode or IZO electrode is formed.

The color liquid crystal display element provided with the colored hardened film of the present invention may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp). Examples of the white LED include a white LED that obtains white light by combining red LEDs, green LEDs, and blue LEDs and combining colors, and a white LED that combines white LEDs by combining blue LEDs, red LEDs, and green phosphors. Light white LED, white LED obtained by combining blue LED, red light-emitting phosphor and green light-emitting phosphor and color mixing to obtain white light, and white light obtained by color mixing of blue LED and YAG-based phosphor White LED, white LED by combining blue LED, orange light-emitting phosphor, and green light-emitting phosphor, and mixing them to obtain white light, by combining ultraviolet LED, red light-emitting phosphor, and green light-emitting phosphor White LED, etc., which is mixed with blue light-emitting phosphor to obtain white light.

In the color liquid crystal display device having the colored hardened film of the present invention, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Planes Switching) type, VA (Vertical Alignment) type, and OCB ( Optically Compensated Birefringence).

The organic EL display element provided with the colored cured film of the present invention may have a suitable structure. For example, a structure disclosed in Japanese Patent Application Laid-Open No. 11-307242 may be mentioned.

Moreover, the electronic paper provided with the colored hardened film of this invention can take a suitable structure, For example, the structure disclosed by Unexamined-Japanese-Patent No. 2007-41169 is mentioned.

[Example]

Examples are given below to further specifically describe the embodiments of the present invention. However, the present invention is not limited to the following examples.

<Synthesis of this colorant> Synthesis Example 1

20 parts by mass of the compound represented by the following formula (1) and 200 parts by mass of N-dodecylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed under light-shielding conditions, and the obtained solution was stirred at 110 ° C. for 6 hours. . The obtained reaction solution was cooled to room temperature, and then added to a mixed solution of 800 parts by mass of water and 50 parts by mass of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystals were suction-filtered, and the obtained residue was dried to obtain 24 parts by mass of a compound represented by the formula (A-1). From the MS spectrum, it was confirmed that the obtained red solid was a compound represented by the following formula (A-1). The obtained compound was used as a colorant (A-1).

Comparative Synthesis Example 1

Synthesis of a mixture of compounds represented by the following formulae (a-1-1) to (a-1-5) was performed according to the description of Synthesis Example 1 of Japanese Patent Application Laid-Open No. 2010-254964. The obtained compound mixture was used as a colorant (a-1).

Comparative Synthesis Example 2

According to the description of Synthesis Example 2 of Japanese Patent Application Laid-Open No. 2012-181505, a compound represented by the following formula (a-2) was synthesized. The obtained compound was used as a colorant (a-2).

<Preparation and Evaluation of Dye Solution> Preparation Example 1

5 parts by mass of the colorant (A-1) and 95 parts by mass of cyclohexanone as a solvent were mixed to prepare a dye solution (A-1).

Preparation Examples 2 ~ 7

In Preparation Example 1, a coloring agent represented by the following formulae (A-2) to (A-14) was used in place of the colorant (A-1), and a dye solution was prepared in the same manner as in Preparation Example 1. (A-2) ~ (A-14).

Preparation Examples 15 ~ 16

In Preparation Example 1, the colorant (a-1) to the colorant (a-2) were used instead of the colorant (A-1), and the same procedure as in Production Example 1 was performed to prepare a dye solution (a-1). ) ~ Dye solution (a-2).

<Preparation of Pigment Dispersion> Preparation Example 17

15 parts by mass of CI Pigment Blue 15: 6 as a colorant, 12.5 parts by mass of BYK-LPN21116 (manufactured by BYK) as a dispersant (solid content concentration of 40% by mass), and propylene glycol monomethyl ether acetic acid as a solvent 72.5 parts by mass of the ester was treated with a bead mill to prepare a pigment dispersion liquid (a-3).

<(B) Synthesis of Binder Resin> Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was added, and nitrogen substitution was performed. Heat at 80 ° C. and add 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 dropwise at the same temperature 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, succinic acid mono (2-propenyloxy) A mixed solution of 15 parts by mass of ethyl ester) and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile), and the polymerization was maintained at this temperature for 2 hours. After that, the temperature of the reaction solution was raised to 100 ° C, and polymerization was performed for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The obtained binder resin had Mw of 12,200 and Mn of 6,500. This adhesive resin is referred to as "adhesive resin (B1)".

<Preparation and Evaluation of Coloring Composition> Example 1

46.0 parts by mass of a pigment dispersion liquid (a-3), 24.3 parts by mass of a dye solution (A-1), 24.6 parts by mass of a binder resin (B1) solution as a binder resin, and East Asia Synthetic Co., Ltd. as a crosslinking agent M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 7.1 parts by mass of 2-benzyl-2-dimethylamino-1- (4-N- 2.1 parts by mass of phosphonophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, trade name IRGACURE369), 0.05 parts by mass of MEGAFACE F-554 (manufactured by DIC Corporation) as a surfactant, and lactic acid as a solvent Ethyl ester to prepare a colored composition having a solid content concentration of 20% by mass.

The obtained colored composition was applied on a glass substrate using a spin coater, and then pre-baked on a hot plate at 80 ° C. for 10 minutes to form a coating film of three sheets having different film thicknesses.

Next, after the substrate was cooled to room temperature, the high-pressure mercury lamp was used to expose the coating film with radiation having a wavelength of 365 nm, 405 nm, and 436 nm at an exposure amount of 2,000 J / m ² without a mask. As described above, a blue cured film for evaluation was formed on the substrate.

Comparative evaluation

The substrate on which the hardened film was formed was clamped by two deflector plates, and irradiated with a fluorescent lamp (wavelength range 380 to 780 nm) from the back side, while the deflection plate on the front side was rotated, and a luminance meter LS-100 (Minolta (Manufactured by)) The maximum and minimum values of transmitted light intensity are measured. Then, for each cured film, a value obtained by dividing the maximum value by the minimum value was used as a contrast ratio. root Based on the measurement results, the contrast ratio at the chromaticity coordinate value y = 0.080 was obtained. The evaluation results are shown in Table 1. Furthermore, the larger the numerical value of the contrast ratio, the better.

Evaluation of heat resistance

A color analyzer (MCPD2000, manufactured by Otsuka Electronics Co., Ltd.) was used to measure the chromaticity coordinate values (x, y) and stimulus values (Y) of the CIE color system using a C light source and a 2 degree field of view on a substrate with a cured film formed. .

Next, after baking in a clean oven at 230 ° C for 1 hour, the chromaticity coordinate values (x, y) and stimulus values (Y) were measured, and the color change before and after additional baking was evaluated, that is, ΔE ^* _ab . As a result, a case where ΔE ^* _{ab was} less than 3.0 was evaluated as "◎", a case where 3.0 or more was less than 5.0 was evaluated as "￮", and a case where 5.0 or more was evaluated as "x". The evaluation results are shown in Table 1.

Evaluation of voltage holding ratio

A SiO ₂ film preventing the elution of sodium ions was formed on the surface, and the obtained colored composition was spin-coated on a soda glass substrate having an ITO (indium-tin oxide alloy) electrode vapor-deposited into a predetermined shape. The plate was pre-baked for 1 minute to form a coating film with a film thickness of 2.0 μm. Next, the coating film was exposed at an exposure amount of 700 J / m ² without a photomask. Thereafter, the substrate was immersed in a developing solution containing a 0.04% by mass potassium hydroxide aqueous solution at 23 ° C for 1 minute, and after development, the substrate was washed with ultrapure water and air-dried, and post-baked at 230 ° C for 30 minutes to The coating film hardens to form a permanent hardened film. Next, the substrate on which the permanent hardened film was formed and the substrate in which only the ITO electrode was vapor-deposited into a predetermined shape were bonded with a sealant mixed with 1.8 mm glass beads, and then a liquid crystal (MLC6608) made by Merck was injected to produce a liquid crystal cell. Next, the liquid crystal cell was placed in a constant-temperature layer at 60 ° C, and the voltage holding rate of the liquid crystal cell was measured using a liquid crystal voltage holding rate measurement system (VHR-1A type, TOYO Corporation). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. The voltage holding rate here is a value obtained by using (the liquid crystal cell potential difference after 16.7 milliseconds / the voltage immediately after application). If the voltage retention rate of the liquid crystal cell is 90% or less, the liquid crystal cell cannot maintain the time of 16.7 milliseconds and the applied voltage to a predetermined level, which means that the liquid crystal cannot be fully aligned and may cause "burn-in" such as afterimages.

Examples 2 to 14 and Comparative Examples 1 to 2

In Example 1, the coloring composition was prepared in the same manner as in Example 1 except that the types and amounts of the pigment dispersion liquid and the dye solution were changed as shown in Table 1. The obtained coloring composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Claims (6)

A coloring composition comprising (A) a coloring agent containing a compound having a structure represented by the following formula (1), (B) a binder resin, and (C) a polymerizable compound; [In formula (1), m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of R ⁵ may be the same or different; R ¹ to R ⁴ independently represent a hydrogen atom, substituted or non- A substituted hydrocarbon group, or a substituted or unsubstituted heterocyclic group; however, the hydrocarbon group may have a bonding group selected from among -CO-, -COO-, and -CONH- between CC bonds; R ⁵ each independently represents a monovalent group; however, one or more of R ¹ to R ⁴ are groups selected from the following requirements (i) and (ii); (i) is a substituted or unsubstituted A saturated aliphatic hydrocarbon group, or a substituted or unsubstituted unsaturated alicyclic hydrocarbon group; however, the unsaturated aliphatic hydrocarbon group may have a CC bond selected from -CO-, -COO-, and -CONH- (Ii) an alicyclic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group or an unsaturated alicyclic hydrocarbon group]. The requested item of the colored composition 1, wherein R ⁵ is _{^{-CO 2 -, -CO 2 H,}} -CO 2 M, -CO 2 R 6, -SO 3 -, -SO 3 H, -SO 3 M, - SO ₃ R ⁷ , -SO ₂ NHR ⁸ , -SO ₂ NR ⁹ R ¹⁰ , -SO ₂ -ON = CR ¹¹ R ¹² , -SO ₂ NHNHR ¹³ , -SO ₂ SR ¹⁴ or -SO ₂ NHSO ₂ R ¹⁵ ; R ⁶ to R ¹¹ and R ¹³ to R ¹⁵ are independently a substituted or unsubstituted hydrocarbon group; R ¹² is a hydrogen atom or a substituted or unsubstituted hydrocarbon group; and M is a sodium atom or a potassium atom. The coloring composition according to claim 1 or 2, further comprising at least one selected from the group consisting of a blue pigment, a blue dye, a purple pigment, and a purple dye as a colorant. A colored hardened film formed using the colored composition according to any one of claims 1 to 3. A display element comprising a colored hardened film as claimed in claim 4. A compound having a structure represented by the following formula (1); [In formula (1), m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of R ⁵ may be the same or different; R ¹ to R ⁴ independently represent a hydrogen atom, substituted or non- A substituted hydrocarbon group, or a substituted or unsubstituted heterocyclic group; however, the hydrocarbon group may have a bonding group selected from among -CO-, -COO-, and -CONH- between CC bonds; R ⁵ each independently represents a monovalent group; however, one or more of R ¹ to R ⁴ are groups selected from the following requirements (i) to (ii); (i) substituted or unsubstituted unsaturated Alicyclic hydrocarbon group; (ii) an alicyclic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group or an unsaturated alicyclic hydrocarbon group].