TWI650380B - Coloring composition, coloring cured film, and display element - Google Patents

Abstract

An object of the present invention is to provide a coloring composition suitable for forming a coloring cured film having excellent heat resistance and high contrast.

The solution of the present invention is a coloring composition containing (A) a coloring agent and (B) a polymerizable compound, wherein (A) the coloring agent is selected from a monomer (α3) and a polymer (α4) ) And at least one selected from the group consisting of a monomer (β3) and a polymer (β4), the monomer (α3) having At least one of a chromophore and a cyanine chromophore and a polymerizable group, the polymer (α4) contains the monomer (α3) as a structural unit, and the monomer (β3) has a group selected from triaryl Methane chromophore and anthraquinone chromophore, at least one chromophore and polymerizable group, the polymer (β4) contains the monomer (β3) as a structural unit (excluding (A) coloring When the agent is a combination of the monomer (α3) and the monomer (β3)).

Description

Colored composition, colored cured film and display element

The present invention relates to a colored composition, a colored cured film, and a display element, and more specifically, to a colored composition for forming a colored cured film, a colored cured film formed using the colored composition, and a display including the colored cured film. Element, and the colored cured film is suitable for transmissive or reflective color liquid crystal display elements, solid-state imaging elements, organic EL display elements, electronic paper, and the like.

When manufacturing a color filter using a color-sensitive radiation composition, a method is known in which a pigment-dispersed color-sensitive radiation composition is coated on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape ( Hereinafter, it is referred to as "exposure"), and pixels of each color are obtained by development (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). In addition, 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 liquid crystal display elements and high-definition solid-state imaging elements have been urgently required. In order to realize these demands, technologies using dyes as colorants have been studied. However, in general, compared with the case where a pigment is used as a colorant, Sexual problems mostly. Against such a background, as a coloring composition capable of forming a coloring pattern excellent in heat resistance and the like, for example, Patent Document 5 proposes a coloring composition containing a pigment multimer as a colorant.

[Prior technical literature] [Patent Literature]

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

Patent Document 2: Japanese Patent Application Laid-Open No. 3-52201

Patent Document 3: Japanese Unexamined Patent Publication No. 6-35188

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

Patent Document 5: Japanese Patent Application Publication No. 2013-28764

However, according to research by the present inventors, it has been found that the contrast of a coloring pattern formed using the coloring composition described in Patent Document 5 is extremely low, and is not suitable for each color pixel used in a color filter or the like.

Therefore, an object of the present invention is to provide a coloring composition suitable for forming a coloring cured film having excellent heat resistance and high contrast. Another object of the present invention is to provide a colored cured film formed using the colored composition and a display element including the colored cured film.

As a result of intensive research, the present inventors have found that the above-mentioned problem can be solved by using a specific compound having a site emitting fluorescence and a specific compound having a site absorbing the fluorescence as a colorant.

That is, the present invention provides a coloring composition containing (A) a coloring agent and (B) a polymerizable compound, wherein (A) the coloring agent is selected from a monomer (α1) and a polymer (α2) (Hereinafter, also referred to as “compound group α ¹ ”) and at least one selected from monomer (β1) and polymer (β2) (hereinafter, also referred to as “compound group β ¹ ”) In combination, the monomer (α1) has a fluorescent emitting site and a polymerizable group, and the polymer (α2) contains the above-mentioned monomer (α1) as a structural unit, and the monomer (β1) has And a polymerizable group, the polymer (β2) contains the above-mentioned monomer (β1) as a structural unit, and does not include (A) a colorant which is a combination of the above-mentioned monomer (α1) and the above-mentioned monomer (β1) Happening.

In addition, the present invention provides a coloring composition containing (A) a coloring agent and (B) a polymerizable compound, wherein (A) the coloring agent is selected from a monomer (α3) and a polymer (α4) (Hereinafter, also referred to as “compound group α ² ”) and at least one selected from monomer (β3) and polymer (β4) (hereinafter, also referred to as “compound group β ² ”) Combination, the monomer (α3) has a member selected from At least one of a chromophore and a cyanine chromophore and a polymerizable group, the polymer (α4) contains the monomer (α3) as a structural unit, and the monomer (β3) has a group selected from triaryl Methane chromophore and anthraquinone chromophore, at least one kind of chromophore and polymerizable group, the polymer (β4) contains the monomer (β3) as a structural unit, and (A) coloring is not included When the agent is a combination of the monomer (α3) and the monomer (β3).

Here, the polymer containing a monomer as a structural unit may be a homopolymer or a copolymer as long as it has the monomer as an essential structural unit. Hereinafter, the “compound group α ¹ and the compound group α ² ” may be referred to as a “compound group α”, the “compound group β ¹ and the compound group β ² ” may be referred to as a “compound group β”, and the “monomer (α1 ) And monomer (α3) "are called" monomer α "," monomer (β1) and monomer (β3) "are called" monomer β ", and" polymer (α2) "and polymer (α4) ") Is called" Polymer α ", and" Polymer (β2) and Polymer (β4) "is called" Polymer β ".

Moreover, this invention provides the colored hardened film formed using the said coloring composition, and the display element provided with this colored hardened film. Here, the "colored cured film" refers to pixels of each color, a black matrix, a black spacer, and the like used in a display element and a solid-state imaging element.

By using the coloring composition of the present invention, a coloring cured film having excellent heat resistance and high contrast can be formed.

Therefore, the coloring composition of the present invention is extremely suitable for producing a color liquid crystal display element, an organic EL display element, a display element such as electronic paper, and a solid-state imaging element such as a CMOS image sensor.

[Form of Implementing Invention]

Hereinafter, the present invention will be described in detail.

[Coloring composition]

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

-(A) Colorant-

The coloring composition of the present invention contains as a colorant a combination of at least one selected from the compound group α and at least one selected from the compound group β.

Compound Group α α group in compound ¹ is: a monomer having a site to a fluorescent group and a polymerizable group (α1), and comprising the monomer (alpha] l) as a structural unit of the polymer (α2). Examples of the site emitting fluorescence include, for example, Chromophore, cyan chromophore. As a preferable aspect of the compound group α ¹ , a compound selected from Monomer (α3) of at least one chromophore and polymerizable group among chromophores and cyanine chromophores, and polymer (α4) (compound group α ² ). Examples of the polymerizable group include an ethylenically unsaturated group, an ethylene oxide group, an oxetanyl group, and an N-alkoxymethylamino group. Among them, an ethylenically unsaturated group is preferred. Preferred examples of the monomer (α1) include an ethylenically unsaturated monomer having a site that emits fluorescence, and more preferably a monomer selected from the group consisting of The ethylenically unsaturated monomer of at least one of the chromophore and the cyanine chromophore can be represented by the following formula (1-1), for example.

[In the formula (1-1), R ¹ each independently represents a hydrogen atom or a methyl group.

X ¹ each independently represents a divalent hydrocarbon group directly bonded, substituted or unsubstituted, or a divalent group obtained by combining the divalent hydrocarbon group with one or more linking groups containing atoms other than carbon atoms and hydrogen atoms. group.

P indicates a part where fluorescence is emitted.

g represents an integer of 1 or more. ]

Further, the compounds of group β ¹ β group of compounds are: monomers having a phosphor absorbing site monomer (alpha] l) and emitted polymerizable group (beta1), and comprising the monomer (beta1) as a structural unit Polymer (β2). Examples of the site that absorbs the fluorescent light emitted from the monomer (α1) include a triarylmethane chromophore and an anthraquinone chromophore. Preferred embodiments of the compound group β ¹ include a monomer (β 3) having at least one chromophore and a polymerizable group selected from a triarylmethane chromophore and an anthraquinone chromophore, And a polymer (β4) containing the monomer (β3) as a structural unit (compound group β ² ). Examples of the polymerizable group include the same groups as those exemplified for the compound group α, and an ethylenically unsaturated group is preferred. As a preferable aspect of the monomer (β1), an ethylenically unsaturated monomer having a site that absorbs the fluorescence emitted by the monomer (α1) can be mentioned, and more preferably, it has a group selected from a triarylmethane chromophore and anthracene The ethylenically unsaturated monomer of at least one chromophore in the quinone chromophore can be represented by the following formula (1-2), for example.

[In formula (1-2), R ² represents a hydrogen atom or a methyl group.

X ² represents a divalent hydrocarbon group which is directly bonded, substituted or unsubstituted, or a combination of the divalent hydrocarbon group and one or more linking groups containing atoms other than carbon atoms and hydrogen atoms.

Q represents a part that absorbs fluorescence.

h represents an integer of 1 or more. ]

The symbols in the formulae (1-1) and (1-2) will be described below.

R ¹ and R ² may be appropriately selected from a hydrogen atom or a methyl group.

Examples of the divalent hydrocarbon group related to X ¹ and X ² include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. In addition, in this specification, "alicyclic hydrocarbon group" is a concept which excludes the aliphatic hydrocarbon group which does not have a cyclic structure. The divalent aliphatic hydrocarbon group may have any form of a straight chain or a branched chain, and the divalent aliphatic hydrocarbon group and the divalent alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, in this specification, "alicyclic hydrocarbon group" and "aromatic hydrocarbon group" are not only a group consisting only of a ring structure, but also a group in which the ring structure is further substituted for a divalent aliphatic hydrocarbon group. It is sufficient that the structure contains at least an alicyclic hydrocarbon or an aromatic hydrocarbon.

Examples of the divalent aliphatic hydrocarbon group include an alkanediyl group and an alkenediyl group. The number of carbon atoms is preferably 1 to 20, more preferably 2 to 12, and even more preferably 2 to 6. Specific examples include methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, 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, 2-methylpropane-1,2-diyl, 2,2-dimethylpropane-1,3-diyl, ethylene-1,1-diyl, ethylene- 1,2-diyl, propylene-1,2-diyl, propylene-1,3-diyl, propylene-2,3-diyl, 1-butene-1,2-diyl, 1-butene -1,3-diyl, 1-butene-1,4-diyl, 2-pentene-1,5-diyl, 3-hexene-1,6-diyl, and the like.

Examples of the divalent alicyclic hydrocarbon group include a cycloalkyl group and a cycloalkenyl group. Among them, the number of carbon atoms is preferably 3 to 20, and even more preferably 3 to 12. Specific examples include monocyclic hydrocarbon rings such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl. Base, 1,4-extend 1,4-norbornylene, 2,5-extend Basic extension Groups, bridged hydrocarbon groups such as 1,5-adamantyl and 2,6-adamantyl.

Examples of the divalent aromatic hydrocarbon group include an arylene group, and a monocyclic to tricyclic arylene group having 6 to 14 carbon atoms is preferred. Specific examples include phenylene, phenylene, naphthyl, phenanthryl, and anthracenyl.

Moreover, as a divalent group which combined the divalent hydrocarbon group and one or more linking groups containing atoms other than a carbon atom and a hydrogen atom, as a linking group, -O-, -S- is mentioned, for example. , -SO _2- , -CO-, -COO-, -OCO-, -CONR ^3- (R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -NR ^3- (R ³ has the above meaning The same) may have one kind or two or more kinds. The bonding position of the linking group is arbitrary, and may exist, for example, between the ends of the divalent hydrocarbon group or the CC bond. Among them, it is preferably located between one terminal or the CC bond. The divalent hydrocarbon group may be bonded to the linking group to form a ring structure. In addition, the number of carbon atoms mentioned in the paragraph [0020] refers to the total number of carbon atoms in a portion other than the carbon atoms constituting the linking group.

Specific examples of the divalent hydrocarbon group having the above-mentioned linking group between CC bonds include, for example, -CH ₂ -CH ₂ -CH ₂ -COO-CH ₂ -CH _2- , -CH ₂ -CH (-CH ₃ ) -CH ₂ -COO-CH ₂ -CH _2- , -CH ₂ -CH ₂ -CH ₂ -OCO-CH ₂ -CH _2- , -CH ₂ -CH ₂ -CH ₂ -CH ₂ -COO-CH _2- CH (CH ₂ -CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH _2- , -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH (CH ₂ -CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH ₂ -,-(CH ₂ ) ₅ -COO- (CH ₂ ) ₁₁ -CH _2- , -CH ₂ -CH ₂ -CH ₂ -C- (COO-CH ₂ -CH ₃ ) ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH _2- , -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -,-(CH ₂ -CH ₂ -O) _n -CH _2- (n is an integer from 1 to 8),-(CH ₂ -CH ₂ -CH ₂ -O) _m -CH _2- (m is an integer from 1 to 5), -CH ₂ -CH (CH ₃ )- O-CH ₂ -CH _2- , -CH ₂ -CH- (OCH ₃ )-, -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -O-CH ₂ -CH (CH ₂ -CH ₃ )- CH ₂ -CH ₂ -CH ₂ -CH _2- , -CH ₂ -CH ₂ -CH ₂ -O-CO-CH ₂ -CH (CH ₂ -CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH (CH ₂ -CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -NH-COO-CH ₂ -CH _2- , -CH ₂ -CH ₂ -OCO-CH _2- , etc., but are not limited to these groups.

In addition, specific examples of the group having a ring structure in which a divalent hydrocarbon group is bonded to the linking group include the following groups, but the group is not limited to these groups.

Examples of the substituent possessed by the divalent hydrocarbon group include a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkoxy group may have any of linear and branched forms, and the number of carbon atoms is preferably 1 to 6. Specific examples include methoxy, ethoxy, propoxy, and butoxy. The aryloxy group is preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof include a phenoxy group and a benzyloxy group. Examples of the substituent of the alkoxy group and the aryloxy group include a halogen atom, a nitro group, a hydroxy group, an amine group, a carboxyl group, and a sulfanyl group. When the divalent hydrocarbon group is a divalent aromatic hydrocarbon group, it may be substituted with a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. The number of carbon atoms of the alkyl group and the alkenyl group is preferably 1 to 6, and specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and secondary butyl. Examples of the alkenyl group include vinyl, 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 2 and the like. - Ethyl-2-butenyl and the like. In addition, as a substituent of an alkyl group and an alkenyl group, the same thing as the substituent of the said divalent hydrocarbon group is mentioned.

The P is not particularly limited as long as it is a group derived from a compound that emits fluorescence, and is preferably Chromophore or cyan chromophore. Should be explained, The chromophore or cyanine chromophore is from The residue obtained by removing the g hydrogen atoms of the compound or the cyanine compound is a residue which can be connected to the g X ^{1 of} the formula (1-1).

The Q is not particularly limited as long as it is a group derived from a compound that absorbs fluorescence, and is preferably a triarylmethane chromophore or an anthraquinone chromophore. It should be noted that the triarylmethane chromophore or anthraquinone chromophore is a residue obtained by removing h hydrogen atoms from a triarylmethane compound or anthraquinone compound. X ² linked residues.

g and h each independently represent an integer of 1 or more, preferably 1 or 2.

As Examples of the compound, cyanine compound, triarylmethane compound, and anthraquinone compound include known dyes classified as dyes (Dye) in the color index (CI; issued by The Society of Dyers and Colourists). As these dyes, acid dyes, direct dyes, basic dyes, salt-making dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. can be used, but they have excellent reactivity and can be easily produced. In terms of the compound represented by the formula (1-1) and the compound represented by the formula (1-2), an acid dye, an oil-soluble dye, and a basic dye are preferably used.

The acid dye is a dye classified as a C.I. acid dye in a color index, and the direct dye is a dye classified as a C.I. direct dye in a color index. As an oil-soluble dye, it is in color Dyes classified as C.I. solvent dyes in the index are dyes classified as C.I. basic dyes in the color index as basic dyes.

The following Compounds, cyanine compounds, triarylmethane compounds, and anthraquinone compounds will be described.

As The compound is preferably a compound having a structure represented by the following formula (2). Specific examples include CI Basic Violet 10 (rhodamine B) and the like. Department of basic dyes.

[In formula (2), R ¹¹ , R ¹² , R ^13, and R ¹⁴ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and the CC bond of the hydrocarbon group contains an atom other than a carbon atom and a hydrogen atom. A linking group, or a substituted or unsubstituted heterocyclic group.

R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

R ¹⁷ represents _{^{-SO 3 -, -SO 3 H,}} -SO 3 M, -SO 3 R 18, -CO 2 -, -CO 2 H, -CO 2 M, -CO 2 R 19, -SO 2 NHR 20 Or -SO ₂ NR ²¹ R ²² .

r represents an integer of 0 to 5, and when r is an integer of 2 or more, a plurality of R ¹⁷ may be the same or different.

R ¹⁸ , R ^19, and R ²⁰ each independently represent a substituted or unsubstituted hydrocarbon group or a group having a linking group containing an atom other than a carbon atom and a hydrogen atom between CC bonds of the hydrocarbon group.

R ²¹ and R ²² each independently represent a substituted or unsubstituted hydrocarbon group, or a group having a linking group containing an atom other than a carbon atom and a hydrogen atom between CC bonds of the hydrocarbon group, or R ²¹ and R ²² each other A substituted or unsubstituted heterocyclic group formed by a bond.

M represents a sodium atom or a potassium atom. ]

Examples of the hydrocarbon group in R ¹¹ to R ¹⁶ and R ¹⁸ to R ²² include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

The aliphatic hydrocarbon group may be saturated or unsaturated, and examples thereof include an alkyl group, an alkenyl group, and an alkynyl group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 15, and particularly preferably 1 to 8. The aliphatic hydrocarbon group may be linear or branched. Examples of the alkyl group include, in addition to the specific examples described above, heptyl, octyl, nonyl, decyl, undecyl, 1-methyldecyl, dodecyl, and 1-methylundecyl. Alkyl, 1-ethyldecyl, tridecyl, tetradecyl, tertiary dodecyl, pentadecyl, 1-heptyloctyl, cetyl, octadecyl, and the like. Examples of the alkenyl group include 2-octenyl, (4-vinyl) -5-hexenyl, and 2-decenyl in addition to the specific examples described above. Examples of the alkynyl group include ethynyl, 1-propynyl, 1-butynyl, 1-pentynyl, 3-pentynyl, 1-hexynyl, and 2-ethyl-2- Butynyl, 2-octynyl, (4-ethynyl) -5-hexynyl, 2-decynyl and the like.

The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 30 carbon atoms. The alicyclic hydrocarbon group may be saturated or unsaturated, and examples thereof include a cycloalkyl group, a cycloalkenyl group, a fused ring hydrocarbon group, a bridged ring hydrocarbon group, a spiro hydrocarbon group, and a cyclic terpene alkenyl group. More specific examples include cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, tertiary butyl cyclohexyl, cycloheptyl, and cyclooctyl; rings such as 1-cyclohexenyl Alkenyl; tricyclic decyl, decahydro-2-naphthyl, adamantyl and other fused ring hydrocarbon groups; tricyclic [5.2.1.0 ^2,6 ] decane-8-yl, pentacyclopentadecyl, iso Bridging cyclic hydrocarbon groups such as alkyl, dicyclopentenyl, tricyclopentenyl, etc .; monovalent groups such as spiro [3,4] heptane and spiro [3,4] octane, with one hydrogen atom removed Hydrocarbyl groups; cyclic terpene alkene groups such as monovalent groups obtained by removing one hydrogen atom from p-alkane, arborane, pinane, etc. Among the above cycloalkyl and cycloalkenyl groups, the number of carbon atoms is more preferably 3 to 12.

The aromatic hydrocarbon group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Here, "aryl" refers to a monocyclic to tricyclic aromatic hydrocarbon group, and examples thereof include phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, and 9-fluorenyl. Among them, phenyl is preferred , Naphthyl.

In addition, the hydrocarbon groups in R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ^21, and R ²² may have a bond between CC bonds containing atoms other than carbon atoms and hydrogen atoms. When the group has a linking group, a group having the above-mentioned linking group between CC bonds of the aliphatic hydrocarbon group is preferred. Specific examples of the linking group include the same groups as described above.

The heterocyclic group may be a monocyclic heterocyclic ring or a polycyclic heterocyclic ring. The heterocyclic group may be an unsaturated ring or a saturated ring, and the ring may have two or more heteroatoms (for example, a nitrogen atom, an oxygen atom, and a sulfur atom) of the same or different kinds. The heterocyclic group is preferably a heterocyclic group having 3 to 10 carbon atoms, and examples thereof include pyrrolidinyl, imidazolinyl, pyrazolyl, Phosphono, thio Linyl, piperidinyl, piperidinyl, piperidinyl Base And other nitrogen-containing alicyclic heterocyclic groups, 1,3-dioxolane-2-yl and other alicyclic heterocyclic groups, pyridyl, pyridine Base, pyrimidinyl, Quinolyl, isoquinolyl, phthaloyl Base, naphthyridinyl, quinoxalinyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, benzothiazolyl, Nitrogen-containing aromatic heterocyclic groups such as azolyl, indolyl, indazolyl, benzimidazolyl, phthalimide, and other aromatic heterocyclic groups such as thienyl, furyl, pyranyl, and purine Ring base.

Examples of the heterocyclic group in which R ²¹ and R ²² are bonded to each other include the same groups as those described above.

Examples of the substituent of the hydrocarbon group in R ¹¹ to R ¹⁶ and R ¹⁸ to R ²² include a halogen atom, a hydroxyl group, a cyano group, a methylamino group, a carboxyl group, a nitro group, an amine group, and a bis (C _1-8 alkyl group). ) Amino, diarylamino, C _1-8 alkoxy, C _6-10 aryloxy, C _2-8 alkoxycarbonyl, C _1-8 alkylthio, C _6-10 aryl Thio, tri (C _1-8 alkyl) silyl, mercapto, allyl, C _1-8 alkylsulfonyl, C _1-8 alkylsulfamoyl, heterocyclyl, aromatic hydrocarbon Etc., alicyclic hydrocarbon groups, heterocyclic groups and aromatic hydrocarbon groups may be substituted with aliphatic hydrocarbon groups. These substituents may further have a substituent. 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. Incidentally, a substituted heterocyclic group as R ¹¹ ~ R ¹⁴ heterocyclyl substituents involved and R ²¹ and R ²² bonded to each other is formed, and may include R ¹¹ ~ R ¹⁶ and R ¹⁸ ~ R The substituent of the hydrocarbon group in ²² is the same group.

Among them, R ¹¹ , R ¹² , R ¹³ and R ^{14 are} preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

R ¹⁵ and R ^{16 are} preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

R ^{17 is} preferably -SO ₃ H, -SO ₃ R ¹⁸ , -CO ₂ H, -CO ₂ R ¹⁹ , -SO ₂ NHR ²⁰ or -SO ₂ NR ²¹ R ²² , and R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ^{22 are} preferably an alkyl group having 1 to 8 carbon atoms.

r is preferably 1 or 2.

As having the structure represented by the above formula (2) Specific examples of the compound include a compound having a structure represented by the following formula.

When the structure represented by the above formula (2) is cationic, The compound has an anion to become electrically neutral. Examples of the anion include a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, a methylate anion, and a hydroxide ion.

In addition, when the structure represented by the formula (2) is anionic, The compound has a cation to become electrically neutral. Examples of the cation include a proton, a metal cation, and an onium cation. Examples of the metal cation include monovalent metal cations such as lithium ion, sodium ion, potassium ion, rubidium ion, and cesium ion; and divalent metal cations such as magnesium ion, calcium ion, strontium ion, and barium ion. Examples of onium cations include ammonium cations and sulfonium cations. Specific examples of ammonium cations include cations of compounds described in paragraph [0045] of Japanese Patent Application Laid-Open No. 2011-138094, and specific examples of phosphonium cations include Japanese Patent Laid-Open No. 2013-190776. The cations described in paragraphs [0038] to [0040] and the like.

The cyanine compound is preferably a compound having a structure represented by the following formula (3), and specific examples include a cyanine-based basic dye such as C.I. Basic Red 12.

[In the formula (3), R ³¹ and R ³² each independently represent a substituted or unsubstituted hydrocarbon group.

R ³³ to R ³⁵ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group. A plurality of R ³³ and R ³⁴ may be the same or different.

Ring Z ¹ and ring Z ² each independently represent a substituted or unsubstituted aromatic hydrocarbon ring.

G ¹ and G ² each independently represent -O-, -S-, or -CR ³⁶ R ^37- . Here, R ³⁶ and R ³⁷ each independently represent a substituted or unsubstituted hydrocarbon group.

s represents an integer from 1 to 3. ]

Examples of the hydrocarbon group in R ³¹ to R ³⁷ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. As a specific example, the same group as a hydrocarbon group in Formula (2) can be mentioned, and the same group can also be mentioned as a substituent.

The aromatic hydrocarbon ring of the ring Z ¹ and the ring Z ² may be a monocyclic aromatic hydrocarbon ring or a polycyclic aromatic hydrocarbon ring. The number of carbon atoms is preferably 6 to 20, and more preferably 6 to 10. Specific examples include a benzene ring, a biphenyl ring, a naphthalene ring, a chamomile ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a naphthacene ring, a benzophenanthrene ring, and the like. Examples of the substituent of the aromatic hydrocarbon ring include the same groups as those of the hydrocarbon group in the formula (2).

Among them, the hydrocarbon group in R ³¹ and R ³² is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 6 carbon atoms. .

R ³³ to R ^{35 are} preferably a hydrogen atom.

The ring Z ¹ and the ring Z ^{2 are} preferably a benzene ring.

G ¹ and G ^{2 are} preferably -O- and -CR ³⁶ R ^37- , and R ³⁶ and R ^{37 are} preferably alkyl groups having 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Alkyl is particularly preferably methyl or ethyl.

s is preferably 1 or 2, and more preferably 1.

Specific examples of the cyanine compound having a structure represented by the formula (3) include a compound having a structure represented by the following formula.

When the structure represented by the formula (3) is cationic, the cyanine compound having the structure has an anion to be electrically neutral. When the structure represented by the formula (3) is anionic, the cyanine compound having the structure has a cation to be electrically neutral. Specific examples of such anions and cations include the same ions as those exemplified in the formula (2).

Examples of the triarylmethane compound include a diaminotriarylmethane-based dye, a triaminetriarylmethane-based dye, and a rosic acid-based dye having an OH group. Among them, diamine triarylmethane is preferred in terms of excellent hue and excellent sunlight fastness than other dyes. Dyes, triamine triarylmethane dyes. As a more preferable triarylmethane compound, the compound which has a structure represented by following formula (4) is mentioned. In addition, although various resonance structures exist in the structure represented by following formula (4), in this specification, these resonance structures are equivalent to the structure represented by following formula (4).

[In formula (4), Y represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or -NR ⁵⁹ R ⁶⁰ .

R ⁴¹ to R ⁴⁴ and R ⁵⁹ to R ⁶⁰ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group.

R ⁴⁵ to R ⁵² represent a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group, or -COOR ' . Here, R ' represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

Ar represents a substituted or unsubstituted aromatic hydrocarbon group. ]

Examples of the hydrocarbon group related to Y, R ⁴¹ to R ⁵² , R ⁵⁹ to R ^60, and R ′ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. As a specific example, the same group as a hydrocarbon group in Formula (2) can be mentioned, and the same group can also be mentioned as a substituent.

The aromatic hydrocarbon group related to Ar is preferably 6 to 20 carbon atoms, more preferably The number of carbon atoms is 6 to 10. Specific examples include phenylene, naphthyl, biphenyl, and anthracenyl. Examples of the substituent of the aromatic hydrocarbon group include the same groups as the substituents of the hydrocarbon group in formula (2). Among them, a halogen atom is preferred.

Among them, R ⁴¹ to R ⁴⁴ , R ⁵⁹ to R ^60, and R ′ are preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

R ⁴⁵ to R ^{52 are} preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms.

Ar is preferably phenylene or naphthyl.

Y is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

In the present invention, among the structures represented by the formula (4), cations represented by the following formula (4-1) or (4-2) are particularly preferred from the viewpoints of heat resistance and solvent resistance.

[In the formulae (4-1) and (4-2), Y ¹ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or -NR ⁶¹ R ⁶² .

R ⁵³ to R ⁵⁶ and R ⁶¹ to R ⁶² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

R ⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms. ]

R ⁵³ to R ^{56 are more} preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

R ⁵⁷ and R ^{58 are} preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.

R ⁶¹ to R ^{62 are} preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Y ^{1 is} preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Specific examples of the triarylmethane compound having a structure represented by the formula (4) include a compound having a structure represented by the following formula.

When the structure represented by the formula (4) is cationic, the triarylmethane compound having the structure has an anion to be electrically neutral. When the structure represented by the formula (4) is anionic, the triarylmethane compound having the structure has a cation to be electrically neutral. Specific examples of such anions and cations include the same ions as those exemplified in the formula (2).

As the anthraquinone compound, a compound having a structure represented by the following formula (5-1) or (5-2) is preferred, and specific examples include C.I. Anthraquinone-based oil-soluble dyes such as Solvent Green 3.

[In the formula (5-1), R ⁷¹ and R ⁷² each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group. ]

[In the formula (5-2), R ⁸¹ and R ⁸² represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

R ⁸³ represents a substituted or unsubstituted divalent hydrocarbon group.

R ⁸⁴ , R ⁸⁵ and R ⁸⁶ each independently represent a substituted or unsubstituted hydrocarbon group. ]

Examples of the hydrocarbon group in R ⁷¹ , R ⁷² , R ⁸¹ , R ⁸² and R ⁸⁴ to R ⁸⁶ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples include the same groups as those exemplified in the formula (2), and the same groups may be used as the substituents.

^Examples of the divalent hydrocarbon group in R ⁸³ include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. Specific examples include the same groups as those exemplified for the divalent hydrocarbon groups according to the formulae (1-1) and (1-2), and the same groups may be mentioned as the substituents.

Among them, R ⁷¹ and R ^{72 are} preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and more preferably hydrogen. Atoms are either substituted or unsubstituted phenyl. Examples of the substituent of the alkyl group include a halogen atom, a hydroxyl group, and a cyano group. Examples of the substituent of the aryl group and the phenyl group include a halogen atom, a hydroxyl group, a cyano group, and an alkyl group having 1 to 6 carbon atoms. Base etc.

As R ⁸¹ , R ⁸² , R ⁸⁴ , R ⁸⁵ and R ⁸⁶ , a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms is preferable, and a hydrogen atom or a substituted or unsubstituted carbon atom is more preferable. Alkyl number 1-4. Examples of the substituent of the alkyl group include the same groups as described above.

R ^{83 is} preferably an alkanediyl group having 1 to 20 carbon atoms, and more preferably an alkanediyl group having 2 to 8 carbon atoms. Examples of the substituent of the alkanediyl group include the same groups as the substituents of X ¹ and X ² according to the formulae (1-1) and (1-2).

Specific examples of the anthraquinone compound having a structure represented by the formula (5-1) or (5-2) include a compound having a structure represented by the following formula.

In addition to the above, as For the compound, for example, the following dyes can be used: CI Acid Red 51 (Erythrosine), CI Acid Red 52 (Acid Rhodamine), CI Acid Red 87 (Eosin G), CI Acid Red 92 (Acid Fluorescent Pink PB) ), CI Acid Red 87 (Eosin G), CI Acid Red 92 (Acid Fluorescent Peach PB), CI Acid Red 289, CI Acid Red 388, Bengal Red B (Food Red No. 5), Acid Rhodamine G, CI Acid Violet 9 etc. Series acid dyes; CI solvent red 35, CI solvent red 36, CI solvent red 42, CI solvent red 43, CI solvent red 44, CI solvent red 45, CI solvent red 46, CI solvent red 47, CI solvent red 48, CI Solvent Red 49, CI Solvent Red 72, CI Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, CI Solvent Violet 10, etc. Oil-soluble dyes; CI Basic Red 1 (Rhodamine 6GCP), CI Basic Red 8 (Rhodamine G), etc. Department of basic dyes.

In addition, as the cyanine compound, for example, CI basic red 13, CI basic red 14, CI basic violet 7, CI basic yellow 11, CI basic yellow 13, CI basic yellow 21, and CI basic can be used. Anthocyanine-based basic dyes such as Yellow 28 and CI Basic Yellow 51.

In addition, as the triarylmethane compound, for example, the following dyes can be used: CI acid blue 1, CI acid blue 3, CI acid blue 5, CI acid blue 7, CI acid blue 9, CI acid blue 11, CI acid blue 15 , CI acid blue 17, CI acid blue 19, CI acid blue 22, CI acid blue 24, CI acid blue 38, CI acid blue 48, CI acid blue 75, CI acid blue 83, CI acid blue 90, CI acid blue 91 , CI acid blue 93, CI acid blue 93: 1, CI acid blue 100, CI acid blue 103, CI acid blue 104, CI acid blue 109, CI acid blue 110, CI acid blue 119, CI acid blue 147, CI acid Blue 269, CI Acid Blue 123, CI Acid blue 213, CI direct blue 41, CI acid violet 17, CI acid violet 19, CI acid violet 21, CI acid violet 23, CI acid violet 25, CI acid violet 38, CI acid violet 49, CI acid violet 72, etc. Methane-based acid dyes; CI Basic Violet 1 (methyl violet), CI Basic Violet 3 (crystal violet), CI Basic Violet 14 (Magenta), CI Basic Blue 1 (basic cyanine 6G), CI Basic Blue 5 (Alkaline Cyan EX), CI Basic Blue 7 (Victoria Pure Blue BO), CI Basic Blue 26 (Victoria Blue B conc.), CI Basic Green 1 (Bright Green GX), CI Basic Triarylmethane-based basic dyes such as sex green 4 (peacock green); triarylmethane-based direct dyes such as CI Direct Blue 41.

In addition, as the anthraquinone compound, for example, the following dyes can be used: CI acid blue 23, CI acid blue 25, CI acid blue 27, CI acid blue 35, CI acid blue 40, CI acid blue 41, CI acid blue 43, CI acid blue 45, CI acid blue 47, CI acid blue 49, CI acid blue 51, CI acid blue 53, CI acid blue 55, CI acid blue 56, CI acid blue 62, CI acid blue 68, CI acid blue 69, CI Acid Blue 78, CI Acid Blue 80, CI Acid Blue 81: 1, CI Acid Blue 11, CI Acid Blue 124, CI Acid Blue 127, CI Acid Blue 127: 1, CI Acid Blue 140, CI Acid Blue 150, CI Acid blue 175, CI acid blue 215, CI acid blue 230, CI acid blue 277, CI acid blue 344, CI acid violet 41, CI acid violet 42, CI acid violet 43, CI acid green 25, CI acid green 27, etc. Quinone-based acid dyes; CI Direct Violet 17 and other direct dyes; CI Solvent Red 172, CI Solvent Red 222, CI Solvent Violet 60, etc. Quinone-based oil-soluble dyes and the like.

The method for synthesizing monomer α and monomer β is not particularly limited, and a conventionally known method can be used. For example, the compound represented by the formula (1-1) and the compound represented by the formula (1-2) can be obtained by introducing an ethylenically unsaturated group into the basic skeleton of the dye having a functional group by a general organic synthesis method. The dye is synthesized by introducing a group having an ethylenically unsaturated group into a synthetic raw material of the dye. More specifically, reference may be made to the descriptions of Japanese Patent Application Laid-Open No. 2013-178478, Japanese Patent Application Laid-Open No. 2013-173850, Japanese Patent Application Laid-Open No. 2013-210621, Japanese Patent Application Laid-Open No. 2013-028764, and the like.

By polymerizing the monomer α and the monomer β, the polymer α and the polymer β can be produced separately. For the polymerization reaction, a conventionally known method can be used, and for example, the same method as the (C) binder resin described later can be used.

The polymer α and the polymer β may each have a copolymerizable ethylenically unsaturated monomer (hereinafter, also referred to as “unsaturated monomer (a3)”) as a structural unit other than the monomer α and the monomer β. .

Specific examples of such an unsaturated monomer (a3) include (meth) acrylic acid, maleic acid, maleic anhydride, and succinic acid mono [2- (meth) acryloxyethyl] Esters, ω-carboxy polycaprolactone mono (meth) acrylates, ethylenically unsaturated monomers with carboxyl groups such as p-vinylbenzoic acid; N-phenylmaleimide, N-cyclohexyl horse N-substituted maleimide such as lyme imine; styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether , Aromatic vinyl compounds such as pinene; methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate Esters, 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 glycol (polymerization degree 2 ~ 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 ~ 10) mono (meth) acrylate, (meth) acrylate cyclohexyl Ester, (meth) acrylic acid Ester, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, (meth) acrylic acid 4-hydroxyphenyl ester, ethylene oxide modified (meth) acrylate of p-cumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, 3 -((Meth) acryloxymethyl] oxetane, 3-[(meth) acryloxymethyl] -3-ethyloxetane, etc. Acrylate; cyclohexyl vinyl ether, iso Vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3- (vinyloxymethyl) -3-ethyl Vinyl ethers such as oxetane; have at the ends of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly (butyl) (meth) acrylate, polysiloxane Mono (meth) acrylfluorenyl macromonomer.

Among these, from the viewpoints of heat resistance, solvent resistance, migration control, and dispersibility, the unsaturated monomer (a3) is preferably an ethylenically unsaturated monomer having a carboxyl group and a (meth) acrylate.

Polymer α and polymer β are made of unsaturated monomer (a3). When it is a copolymer of a structural unit, it is preferable that the copolymerization ratio of the unsaturated monomer (a3) in all the structural units of the polymer (alpha) and the polymer (beta) is as follows. That is, the copolymerization ratio of the unsaturated monomer (a3) in all the structural units is preferably 30 to 97% by mass, more preferably 40 to 95% by mass, and particularly preferably 50 to 90% by mass. By copolymerizing the unsaturated monomer (a3) in such a range, a colored composition having excellent heat resistance, solvent resistance, migration control, and dispersibility is easily obtained.

The weight average molecular weight (Mw) of polymer α and polymer β measured by gel permeation chromatography (hereinafter referred to as GPC) (eluting solvent: tetrahydrofuran) in terms of polystyrene is usually 1000 to 100,000, preferably It is 3,000 to 50,000, and more preferably 3,000 to 10,000. By adopting this method, the contrast, heat resistance, solvent resistance, migration resistance, coating characteristics, electrical characteristics, pattern shape, and resolution can be improved.

In addition, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer α and the polymer β is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0. In addition, Mn mentioned here is a number average molecular weight in polystyrene conversion measured by GPC (eluting solvent: tetrahydrofuran).

In the present invention, as the (A) colorant, a combination of at least one selected from the compound group α and at least one selected from the compound group β is included, but from the viewpoint of contrast, the compound group α is preferred It is a state in which the polymer α and the compound group β are monomer β. Further, from the viewpoint of heat resistance, it is preferable that the compound group α is a polymer α and the compound group β is a monomer β, or the compound group α is a polymer α and the compound group β is a polymer β. In addition, from the viewpoint of solvent resistance, it is preferable that the compound group α is a polymer α and the compound group β is a polymer β. Where from the balance From the viewpoint of achieving high levels of contrast, heat resistance, and solvent resistance, the compound group α is a polymer α and the compound group β is a polymer β.

The content ratio (α / β) of the compound group α to the compound group β is in molar ratio, preferably 99/1 to 40/60, more preferably 98/2 to 60/40, and still more preferably 97/3 ~ 70/30, especially preferred is 96/4 ~ 80/20.

Especially in a case where the compound group α is a polymer α and the compound group β is a polymer β, the polymer α and the polymer are from the viewpoint of achieving a good balance at a high level of contrast, heat resistance, and solvent resistance. The content ratio of β (α / β) is in molar ratio, preferably 93/7 to 75/25, more preferably 92/8 to 80/20, and still more preferably 91/9 to 85/25.

The coloring composition of the present invention may be used by mixing colorants other than compound group α and compound group β. Other colorants are not particularly limited, and colors and materials can be appropriately selected according to the application. Examples of other colorants include pigments and dyes other than the compound group α and the compound group β. Of course, it may contain a compound having a site emitting fluorescence and not having a polymerizable group. The compound having at least one type of chromophore and cyanine chromophore and having no polymerizable group may also contain a compound having a site that absorbs fluorescence and does not have a polymerizable group. A compound having at least one of a triarylmethane chromophore and an anthraquinone chromophore and having no polymerizable group. Among these, from the viewpoint of obtaining pixels with high brightness, contrast, and tinting power, organic pigments are preferred as the pigments, and organic dyes are preferred as the dyes. Examples of the organic dye include dyes described in paragraphs [0072] to [0075] of the present specification.

Examples of the organic pigment include the following compounds classified as pigments in the color index.

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 Green 59; CI Pigment Blue 15: 6, CI Pigment Blue 16, CI Pigment Blue 80; CI Pigment Yellow 14, 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 Violet 23.

In addition, the red pigment represented by the above formula, Japanese Patent Laid-Open No. 2001-081348, Japanese Patent Laid-Open No. 2010-026334, Japanese Patent Laid-Open No. 2010-237384, and Japanese Patent Laid-Open No. 2010-237569 can be cited. The lake pigments described in Japanese Patent Application Publication No. 2011-006602, Japanese Patent Application Publication No. 2011-145346, and the like.

In the present invention, other pigments that are arbitrarily mixed may be refined and used 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 their particles with a resin as necessary. Examples of the resin that modifies the surface of the pigment particles include a vehicle resin described in Japanese Patent Application Laid-Open No. 2001-108817 or various commercially available resins for pigment dispersion. As a resin coating method on the surface of carbon black, for example, the methods described in Japanese Patent Application Laid-Open No. 9-71733, Japanese Patent Application Laid-Open No. 9-95625, Japanese Patent Application Laid-Open No. 9-124969, and the like can be used. The organic pigment can be used by miniaturizing the primary particles by a so-called salt mill. As a method of salt milling, for example, the method disclosed in Japanese Patent Application Laid-Open No. 8-179111 can be used.

In addition, in the present invention, a known dispersant and a dispersing aid may be further contained in addition to other colorants arbitrarily mixed. Examples of well-known dispersants include polyurethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene alkylphenyl ether-based dispersants, Polyethylene glycol diester-based dispersants, sorbitan fatty acid ester-based dispersants, polyester-based dispersants, acrylic-based dispersants, and the like, and examples of the dispersion aid include pigment derivatives.

Such dispersants are commercially available. Examples of the acrylic dispersants include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above , Manufactured by BYK-Chemie (BYK)) and the like, as the polyurethane-based dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 ( Above, BYK-Chemie (BYK)), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), etc. As the polyethyleneimine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc., as polyester dispersant Examples include Adisper PB821, Adisper PB822, Adisper PB880, Adisper PB881 (above, manufactured by Ajinomoto Fine-Techno Co., Ltd.), and BYK-LPN21324 (manufactured by BYK-Chemie (BYK)).

Examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinophthalone.

In the present invention, other colorants may be used alone or in combination of two or more.

When other colorants are contained, the content ratio of the other colorants is preferably 70% by mass or less, and more preferably 50% by mass or less with respect to the total content of the colorants. The lower limit value is not particularly limited, but may be 0.01% by mass or more.

In view of forming a pixel having high heat resistance, solvent resistance, migration control, high brightness and excellent color purity, or a black matrix and black spacer having excellent light shielding properties, the content ratio of the (A) colorant is usually The solid content is 3 to 70% by mass, preferably 5 to 60% by mass, and even more preferably 5 to 30% by mass. Here, a solid content is a component other than the solvent mentioned later.

-(B) polymerizable compound-

The polymerizable compound in the present invention 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, the polymerizable compound is preferably a compound having two or more (meth) acrylfluorenyl groups or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acrylfluorenyl groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, and modified with caprolactone. Polyfunctional (meth) acrylates, polyfunctional (meth) acrylates modified with alkylene oxides, and polyfunctional polyurethanes obtained by reacting hydroxyl (meth) acrylates with polyfunctional isocyanates 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.

Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; glycerol, trimethylolpropane, pentaerythritol, and dipentaerythritol. A trivalent or higher 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, glycerol dimethacrylate and the like. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and the like. As acid anhydride, Examples include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, dibasic acid anhydrides, pyromellitic dianhydride, and biphenyl. Tetracarboxylic dianhydride such as tetracarboxylic 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 polyfunctional (meth) acrylate modified with the alkylene oxide include bisphenol A di (meth) acrylate modified with at least one selected from the group consisting of ethylene oxide and propylene oxide. Isocyanuric acid tri (meth) acrylate modified with at least one kind selected from ethylene oxide and propylene oxide, and modified with at least one kind selected from ethylene oxide and propylene oxide Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, selected from ethylene oxide and At least one modified pentaerythritol tetra (meth) acrylate in propylene oxide, at least one modified dipentaerythritol penta (meth) acrylate selected from ethylene oxide and propylene oxide, At least one kind of modified dipentaerythritol hexa (meth) acrylate and the like 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, a melamine structure and a benzoguanamine structure mean that it has 1 or more Ring or phenyl substituted tri The chemical structure of a ring as a basic skeleton is a concept including melamine, benzoguanamine, or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ' , N ' , N " , N " -hexa (alkoxymethyl) melamine, N , N, N ', N' - tetra (alkoxymethyl) benzoguanamine, N, N, N ', N' - tetra (alkoxymethyl) glycoluril and the like.

Among these polymerizable compounds, a polyfunctional (meth) acrylate obtained by reacting a ternary or higher aliphatic polyhydroxy compound with (meth) acrylic acid, or a polyfunctional (meth) modified with caprolactone is preferred. Acrylates, polyfunctional polyurethane (meth) acrylates, polyfunctional (meth) acrylates with carboxyl groups, N, N, N ' , N ' , N " , N " -hexa (alkoxy) yl-methyl) melamine, N, N, N ', N' - tetra (alkoxymethyl) benzoguanamine. Considering that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and dirt and film residues are not easily generated on the substrate and the light-shielding layer in the unexposed portion, the aliphatic polyhydroxy compound having a valence of 3 or more and (methyl Of the polyfunctional (meth) acrylates obtained by the acrylic acid reaction, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferred. Of the (meth) acrylates, particularly preferred are compounds obtained by reacting pentaerythritol triacrylate and succinic anhydride, and compounds obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride.

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

The content of the (B) polymerizable compound in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 800 parts by mass, and still more preferably 100 to 700 parts by mass relative to 100 parts by mass of the colorant (A). Serving. By setting it as such a way, hardenability and alkaline developability can be made favorable.

-(C) Binder resin-

The coloring composition of the present invention may contain a binder resin (the polymers α and β are not included). Thereby, the alkali solubility of a coloring composition, the adhesiveness with a board | substrate, storage stability, etc. can be improved. The binder resin is not particularly limited as long as it does not belong to the polymers α and β, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among these, a polymer having a carboxyl group (hereinafter referred to as a "carboxyl-containing polymer") is preferred, and examples thereof include an ethylenically unsaturated monomer (hereinafter, referred to as an "unsaturated monomer ( c1) ") is a copolymer of other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as" unsaturated monomers (c2) ").

Examples of the unsaturated monomer (c1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinate mono [2- (meth) acryloxyethyl] ester, and ω-carboxy poly Caprolactone mono (meth) acrylate, p-vinylbenzoic acid and the like.

These unsaturated monomers (c1) can be used individually or in mixture of 2 or more types.

Examples of the unsaturated monomer (c2) include an N-substituted maleimide, an aromatic vinyl compound, a (meth) acrylate, and a vinyl group exemplified in the unsaturated monomer (a3). Ethers, macromonomers having a mono (meth) acrylfluorene group at the end of a polymer molecular chain, and the like, specific examples include the same monomers as described above.

The unsaturated monomer (c2) can be used alone or in combination of two or more.

In the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2), the copolymerization ratio of the unsaturated monomer (c1) in the copolymer is preferably 5 to 50% by mass, and more preferably 10 ~ 40% by mass. By taking this When the unsaturated monomer (c1) is copolymerized in a range, a colored composition having excellent alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2) include, for example, Japanese Patent Application Laid-Open No. 7-140654, Japanese Patent Application Laid-Open No. 8-259876, and Japanese Patent Laid-Open No. 10- Japanese Patent Publication No. 31308, Japanese Patent Application Publication No. 10-300922, Japanese Patent Application Publication No. 11-174224, Japanese Patent Application Publication No. 11-258415, Japanese Patent Application Publication No. 2000-56118, Japanese Patent Application Publication No. 2004-101728, etc. Disclosed copolymers.

In addition, 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. As disclosed in Japanese Unexamined Patent Application Publication No. 11-140144 and Japanese Unexamined Patent Application Publication No. 2008-181095, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylfluorenyl group in a side chain is used as a binder resin.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter referred to as GPC) (eluting solvent: tetrahydrofuran) of the binder resin in the present invention is usually 1,000 to 100,000, preferably It is 3000 ~ 50,000. By adopting such a method, the residual film rate, pattern shape, heat resistance, electrical characteristics, and resolution of the coating film are further improved, and the generation of dry foreign matter at the time of coating can be suppressed at a high level.

In addition, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0. In addition, Mn mentioned here is a number average molecular weight in polystyrene conversion measured by GPC (eluting solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a known method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, and International Publication No. 2007/029871. Control its structure, Mw, Mw / Mn.

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

In the present invention, the content of the (C) binder resin is usually 10 to 1,000 parts by mass, and preferably 20 to 500 parts by mass, relative to 100 parts by mass of the colorant (A). With such an aspect, it is possible to further improve the alkali developability, the storage stability of the colored composition, and the chromaticity characteristics.

-Photopolymerization initiator-

The coloring composition of the present invention may contain a photopolymerization initiator. This makes it possible to impart radiation-sensitive linearity to the colored composition. The photopolymerization initiator used in the present invention is a compound that generates an active material capable of initiating 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 such a 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, polycyclic quinone based compounds, diazonium based compounds, fluorenimine Sulfonate 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 preferably selected from the group consisting of thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, At least one of a system compound and an O-fluorenyl oxime compound.

Among the preferred photopolymerization initiators in 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.

In addition, as a specific example of the acetophenone-based compound, 2-methyl-1- [4- (methylthio) phenyl] -2- Porphyrin-1-one, 2-benzyl-2-dimethylamino-1- (4- Phenolinophenyl) butane-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4- Phenolinyl) butane-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' - bisimidazole, 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.

In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable to use a hydrogen donor together from a point which can improve sensitivity. The "hydrogen donor" as used herein refers to a compound capable of supplying a hydrogen atom to a radical generated from a biimidazole-based compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzo Oxazole mercaptan-based hydrogen donor, 4,4 '- bis (dimethylamino) benzophenone, 4,4' - bis (diethylamino) benzophenone amine-based hydrogen donor . In the present invention, hydrogen donors can be used alone or in combination of two or more, but from the viewpoint of further improving the sensitivity, it is preferable to combine one or more thiol-based hydrogen donors and one or more amine-based donors. Use hydrogen.

Also, as three Specific examples of the system compound include 2,4,6-tris (trichloromethyl) -mesanthine , 2-methyl-4,6-bis (trichloromethyl) -mesan , 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -mesanthine , 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -mesanthine , 2- [2- (4-Diethylamino-2-methylphenyl) vinyl] -4,6-bis (trichloromethyl) -mesanthine , 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -mesanthine , 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -mesanthine , 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -mesanthine , 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -mesanthine Halomethyl Department of compounds.

Specific examples of the O-fluorenyl oxime-based compound include 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzidine oxime), 1 -[9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -ethanone 1- (O-acetamoxime), 1- [9-ethyl- 6- (2-methyl-4-tetrahydrofurylmethoxybenzyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetamoxime), 1- [9-ethyl -6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolyl) methoxybenzyl} -9H-carbazol-3-yl] -Ethyl ketone 1- (O-acetamoxime) and the like. As commercially available products of O-fluorenyl oxime-based compounds, NCI-831, NCI-930 (above, manufactured by ADEKA Co., Ltd.) and the like can also be used.

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. As such sensitizers, include, for example, 4,4 '- bis (dimethylamino) benzophenone, 4,4' - bis (diethylamino) benzophenone, 4- Ethylaminoacetophenone, 4-dimethylaminophenylacetone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5- Bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzyl) coumarin, 4- (diethyl Amine) chalcone and the like.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass with respect to 100 parts by mass of the polymerizable compound (B), and particularly preferably 1 to 100 parts by mass. By setting it as such a way, hardenability and a coating-film characteristic can be made favorable.

-Solvent-

The coloring composition of the present invention contains the above-mentioned components (A) and (B) and other components added arbitrarily, and is usually prepared as a liquid composition by blending an organic solvent.

As the organic solvent, as long as the components (A) and (B) and other components constituting the coloring composition are dispersed or dissolved, and do not react with these components, and have moderate volatility, they can be appropriately selected and used.

Examples of such organic solvents 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 diethyl ether. Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether (Poly) alkylenes such as 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, and tripropylene glycol monoethyl ether Dialkyl glycol monoalkyl ethers; alkyl lactates such as methyl lactate and ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethyl (Cyclo) alkyl alcohols such as hexanol and cyclohexanol; keto alcohols such as diacetone alcohol; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl ether acetates, such as diethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and the like Esters; glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether; cyclic ethers such as tetrahydrofuran; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone Ketones; diacetate such as propylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, etc .; methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate Isoalkoxycarboxylic acid esters; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, butyric acid Ethyl ester, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, propyl Fatty acid alkyl esters such as ethyl ketoacetate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N, N- Amidoamines such as dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone, or lactamamine, and the like.

Among these organic solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene are preferred from the viewpoints of solubility, pigment dispersibility, and coatability. two Alcohol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butane Diethylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl ester, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, Isopropyl butyrate, n-butyl butyrate, ethyl pyruvate and the like.

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

The content of the organic solvent is not particularly limited, and the total concentration of each component other than the organic solvent of the coloring composition is preferably an amount of 5 to 50% by mass, and more preferably an amount of 10 to 40% by mass. With such a configuration, a colorant dispersion liquid having good dispersibility and stability, and a coloring composition having good coatability and stability can be obtained.

-additive-

The coloring composition of this invention may contain various additives as needed.

Examples of the additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); surfactants such as fluorine-based surfactants and silicon-based surfactants; ethylene Trimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethyl Oxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxy Silicon Alkane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxy Adhesion promoters such as silane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane; 2,2-thiobis ( 4-methyl-6-tertiary butylphenol), 2,6-bis (tertiary butyl) phenol and other antioxidants; 2- (3-tertiarybutyl-5-methyl-2-hydroxyphenyl ) -5-chlorobenzotriazole, alkoxybenzophenones and other ultraviolet absorbers; 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 -Propylene glycol, 4-amino-1,2-butanediol and other residue improvers; succinate mono [2- (meth) acryloxyethyl] ester, phthalic acid mono [2- (methyl) ) Developability improvers such as acryloxyethyl] ester and ω-carboxy polycaprolactone mono (meth) acrylate.

[Colored hardened film and its forming method]

The coloring cured film of the present invention is formed using the coloring composition of the present invention, and specifically, it refers to pixels of each color, a black matrix, a black spacer, and the like used in a display element and a solid-state imaging element.

Hereinafter, a coloring cured film used in a color filter constituting a display element and a solid-state imaging element 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 the surface of the substrate so that a portion where a pixel is formed is divided as necessary. Next, on this substrate, for example, a blue liquid composition of the radiation-sensitive colored composition of the present invention is applied, and then a pre-baking is performed to evaporate the solvent to form a coating film. then After exposing the coating film through a photomask, development was performed using an alkaline developer to dissolve and remove the unexposed portions of the coating film. Then, a post-baking is performed to form a pixel array in which blue pixel patterns (colored cured films) are arranged in a predetermined arrangement.

Next, each of the radiation-sensitive coloring compositions in green or red is coated, pre-baked, exposed, developed, and post-baked in the same manner as described above, and a green pixel array is sequentially formed on the same substrate. And red pixel array. Thereby, a color filter in which a pixel array of three primary colors of blue, green, and red is arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the order described above.

The black matrix may be formed by using a photolithography method to form a thin metal film such as chromium by sputtering or vapor deposition into a desired pattern, or a radiation-sensitive coloring composition in which a black colorant is dispersed may be used to form the above-mentioned black matrix. The case of pixels is formed in the same manner.

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

In addition, these substrates may be subjected to appropriate pre-treatments such as a reagent treatment using a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction method, vacuum evaporation, etc., as necessary.

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

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

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

Examples of the light source used to form at least one selected from a pixel and a black matrix include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and medium-pressure mercury. Lamp light source such as lamp, low-pressure mercury lamp, or laser light source such as argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser, etc. As the light source for exposure, an ultraviolet LED may be used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.

The amount of radiation exposure is usually preferably 10 to 10,000 J / m ² .

In addition, as the alkaline developing solution, for example, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4. 0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene and other aqueous solutions.

For example, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol, a surfactant, and the like may be added to the alkaline developer. In addition, after alkaline development, water washing is usually performed.

As the development treatment method, a spray development method, a spray development method, a dip development method, a spin-on immersion (puddle) development method, or the like can be applied. The developing conditions are preferably room temperature and 5 to 300 seconds.

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

The film thickness of the pixel thus formed is usually 0.5 to 5 μm, and preferably 1.0. ~ 3μm.

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

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

In addition, since the partition wall not only functions as a light-shielding function, but also functions to prevent color mixing of the thermosetting coloring composition ejected into the partition area, the film thickness is thicker than the black matrix used in the first method. Therefore, the partition wall is usually formed using a black radiation-sensitive composition.

The substrate used for forming the color filter, the light source of radiation, and the methods and conditions of pre-baking and post-baking are the same as the first method described above. In this way, the film thickness of the pixels formed by the inkjet method is about the same as the height of the partition walls.

After forming a protective film on the pixel pattern obtained in this manner as needed, 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. Spacers usually make It can be formed with a radiation-sensitive composition, and it can also be made into a light-shielding spacer (black spacer). In this case, a radiation-sensitive coloring composition in which a black colorant is dispersed is used, but the coloring composition of the present invention can also be applied to the formation of the black spacer.

The radiation-sensitive coloring composition of the present invention can also be applied to form a colored cured film of each pixel, black matrix, black spacer, or the like used in the color filter.

The color filter containing the colored cured film of the present invention thus formed has extremely high brightness and color purity, and is therefore extremely useful for color liquid crystal display elements, color photographic tube elements, color sensors, organic EL display elements, electronic paper, and the like. In addition, the display element mentioned later may be provided with at least 1 or more colored hardening film formed using the radiation-sensitive coloring composition of this invention.

[Display element]

The display element of the present invention includes the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

The color liquid crystal display element including the colored cured film of the present invention may be a transmissive type or a reflective type, and an appropriate structure may be adopted. For example, a structure in which a color filter is formed on a substrate other than 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 with a liquid crystal layer interposed therebetween. In addition, a substrate having a color filter formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (indium oxide doped with tin) electrode or an IZO (indium oxide and zinc oxide) can also be used. (Mixture) electrode substrate with liquid crystals Layer-opposed structure. The latter structure can significantly increase the aperture ratio, and has the advantage of obtaining a bright and high-definition liquid crystal display element. In the latter configuration, the black matrix and the black spacer may be formed on either 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 including the colored hardened film of the present invention may include a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp) and a backlight unit using a white LED as a light source. Examples of the white LED include a white LED obtained by combining red LEDs, green LEDs, and blue LEDs to obtain white light by mixing colors; a white LED obtained by combining blue LEDs, red LEDs, and green phosphors to obtain white light by mixing colors; Combining blue LED, red light-emitting phosphor and green light-emitting phosphor, white color white LED is obtained by color mixing; white color white LED is obtained by color mixing of blue LED and YAG series phosphor; combined blue LED, Orange LEDs and green LEDs, white LEDs with white light by color mixing; UV LEDs, red LEDs, green LEDs, and blue LEDs are combined to obtain white LEDs by color mixing. White LED and so on.

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

In addition, the organic EL display provided with the colored cured film of the present invention The display element may have a suitable structure, and 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 an appropriate structure, For example, the structure disclosed by Unexamined-Japanese-Patent No. 2007-41169 is mentioned.

[Solid-state image sensor]

The solid-state imaging element of the present invention includes the colored cured film of the present invention. In addition, the solid-state imaging element of the present invention can adopt an appropriate structure. For example, as one embodiment, by using the coloring composition of the present invention and forming a coloring pixel (colored cured film) on a semiconductor substrate such as a CMOS substrate by the same operation as described above, it is possible to produce excellent color separation and color reproducibility. Solid-state imaging element.

[Example]

Hereinafter, examples will be given to explain the embodiments of the present invention in more detail. However, the present invention is not limited to the following examples.

<Synthesis of colorant>

(Synthesis example 1)

A 100 mL three-necked flask equipped with a stirrer and equipped with a reflux cooling tube and a thermometer was sufficiently nitrogen-substituted, 15.0 g of cyclohexanone was added thereto, and the internal temperature was heated to 80 ± 2 ° C. under a nitrogen stream. To maintain the internal temperature at 80 ± 2 ° C, 4.50 g of the pigment monomer (A1) represented by the following formula, 6.00 g of methyl methacrylate, 4.50 g of methacrylic acid, and as the polymerization initiator 2,2 '- azobis (2,4-dimethylvaleronitrile) (Wako pure Chemical industries, Ltd., trade name V-65) 2.18g, and 45.0g cyclohexanone Prepared solution. After completion of the dropwise addition, stirring was continued at this temperature for further 1 hour. After that, the reaction solution was cooled to room temperature, and added dropwise to a large amount of hexane. The obtained colored solid was dried under reduced pressure at 50 ° C to obtain 14.1 g of a polymer (1). Mw of the obtained polymer (1) was 4,800. The polymer (1) corresponds to the polymer α.

Synthesis Examples 2 to 4

In Synthesis Example 1, the polymer (2) was obtained in the same manner as in Synthesis Example 1 except that the kinds and amounts of the monomers used for polymerization were changed as shown in Table 1. ~ (4). The structures of the pigment monomers (A1) to (A4) are as described above. The polymer (2) corresponds to the polymer α, and the polymers (3) to (4) correspond to the polymer β.

The symbols used in Table 1 are as follows.

MMA: methyl methacrylate

MA: methacrylic acid

The pigment monomers (A1) to (A4) were synthesized by referring to the following publications, respectively.

Pigment monomer (A1): Synthesis was performed in accordance with Synthesis Example 2 described in paragraphs [0145] to [0146] of Japanese Patent Application Laid-Open No. 2013-178478. Corresponds to monomer α.

Pigment monomer (A2): Synthesized according to Example 1-1 described in paragraphs [0096] to [0097] of Japanese Patent Application Laid-Open No. 2013-173850. Corresponds to monomer α.

Pigment monomer (A3): Synthesized according to the production of the dye monomer (A1-1) described in paragraphs [0149] to [0150] of Japanese Patent Application Laid-Open No. 2013-210621. Corresponds to monomer β.

Pigment monomer (A4): "Monomer 1" described in paragraph [0501] of Japanese Patent Application Laid-Open No. 2013-028764. Corresponds to monomer β.

<Preparation of colorant solution>

Preparation Example 1

10 parts by weight of the obtained polymer (1) was dissolved in 90 parts by weight of propylene glycol monomethyl ether to prepare a toner solution (A-1).

Preparation Examples 2 ~ 10

In Preparation Example 1, the colorant solutions (A-2) to (A-10) were prepared in the same manner as in Preparation Example 1, except that the types and amounts of the solutes and solvents were changed as shown in Table 2. In addition, in Table 2, the pigment (A5) is C.I. Basic Blue 7 (triarylmethane compound), and the pigment (A6) is an anthraquinone compound represented by the following formula. In addition, propylene glycol monomethyl ether is described as "PGME".

<Synthesis of Binder Resin>

Synthesis Example 5

100 parts by mass of propylene glycol monomethyl ether acetate was added to a flask equipped with a cooling tube and a stirrer, and nitrogen replacement was performed. Heated to 80 ° C, and 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, 5 parts by mass of benzyl methacrylate, and methyl were added dropwise over 1 hour. 15 parts by mass of 2-hydroxyethyl acrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, and mono (2-propenyloxyethyl) succinate and 15 parts by mass of 2,2 '- 6 parts by mass of azobis (2,4-dimethylvaleronitrile) mixed solution, maintaining the temperature polymerization for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and polymerization was performed for an additional hour to obtain a binder resin solution (solid content concentration: 33% by mass). Mw of the obtained binder resin was 12,200 and Mn was 6,500. This adhesive resin is referred to as "adhesive resin (C1)".

<Preparation and Evaluation of Coloring Composition>

[Preparation of coloring composition]

Example 1

(A) 16.5 parts by mass of the toner solution (A-1) and 1.0 part by mass of the colorant solution (A-3), and 23.3 parts by mass of the binder resin (C1) solution as (C) binder resin 9.9 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (product of Nippon Kayaku Co., Ltd., KAYARAD DPHA) as a polymerizable compound, 2-benzyl as a photopolymerization initiator Methyl-2-dimethylamino-1- (4- MEGAFAC F, a fluorosurfactant, 1.8 parts by mass and 0.1 part by mass of NCI-930 (manufactured by ADEKA Co., Ltd.), 1.8 parts by mass and NCI-930 (made by ADEKA Co., Ltd.) -554 (manufactured by DIC Corporation) and 0.05 parts by mass of propylene glycol monomethyl ether acetate as a solvent to prepare a colored composition (S-1) having a solid content concentration of 20% by mass.

[Evaluation of contrast]

After applying the obtained colored composition on a glass substrate using a spin coater, pre-baking was performed on a hot plate at 80 ° C. for 10 minutes to form a coating film having a film thickness of 2.5 μm.

Next, the substrate was cooled to room temperature, and then each coating film was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp at an exposure amount of 2000 J / m ² without a photomask. Thereafter, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was ejected to the substrate at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm) for 90 seconds. Then, the substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 200 ° C. for 30 minutes to form a cured film for evaluation.

The substrate on which the cured film is formed is sandwiched between two polarizing plates, and the front polarizing plate is rotated while being irradiated with a fluorescent lamp (wavelength range of 380 to 780 nm) from the rear side. The luminance meter LS-100 (Minolta Co., Ltd. System) to measure the maximum and minimum values of transmitted light intensity. Then, the value obtained by dividing the maximum value by the minimum value is used as the contrast ratio. The evaluation results are shown in Table 3. In addition, a larger numerical value means a better contrast ratio.

[Evaluation of heat resistance]

The coloring composition (S-1) was coated on a soda glass substrate having a SiO ₂ film preventing the elution of sodium ions using a spin coater, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a 2.5 μm film. Coating film.

Next, the substrate was cooled to room temperature, and then each coating film was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp through a photomask at an exposure amount of 400 J / m ² . Thereafter, a developing solution consisting of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was sprayed onto these substrates at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm), and spray development was performed 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, thereby forming a dot pattern on the substrate.

With respect to the obtained dot pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate values (x, y) and stimulus values (Y) in the CIE color system were measured with a C light source and a 2 degree field of view.

Next, after the substrate was additionally baked at 230 ° C. for 90 minutes, the chromaticity coordinate values (x, y) and stimulus values (Y) were measured, and the color change before and after additional baking was evaluated as ΔE ^* _ab . As a result, a case where the value of ΔE ^* _ab was less than 3.0 was evaluated as "○", a case where 3.0 or more and less than 5.0 was evaluated as "Δ", and a case where 5.0 or more was evaluated as "x". The evaluation results are shown in Table 3. In addition, it can be said that the smaller the ΔE ^* _ab value, the better the heat resistance.

[Evaluation of color change]

The coloring composition (S-1) was coated on a soda glass substrate having a SiO ₂ film preventing the elution of sodium ions using a spin coater, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a 2.5 μm film. Coating film.

Next, the substrate was cooled to room temperature, and then the coating film was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp through a photomask at an exposure amount of 400 J / m ² . Thereafter, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was sprayed on the substrate at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm), and spray development was performed for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230 ° C. for 30 minutes, thereby forming a dot pattern on the substrate.

The substrate was immersed in propylene glycol monomethyl ether acetate at 80 ° C for 40 minutes. The chromaticity coordinate values (x, y) and stimulus values (Y) before and after immersion were measured, and the color change before and after immersion was evaluated as ΔE ^* _ab . As a result, a case where the value of ΔE ^* _ab was less than 3.0 was evaluated as "○", a case where 3.0 or more and less than 5.0 was evaluated as "Δ", and a case where 5.0 or more was evaluated as "x". The evaluation results are shown in Table 3. In addition, it can be said that the smaller the ΔE ^* _ab value, the better the solvent resistance.

[Evaluation of contrast change rate]

The coloring composition (S-1) was coated on a soda glass substrate having a SiO ₂ film preventing the elution of sodium ions using a spin coater, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a 2.5 μm film. Coating film.

Next, the substrate was cooled to room temperature, and then the entire surface of the coating film was exposed to radiation at a wavelength of 365 nm, 405 nm, and 436 nm using an exposure pressure of 400 J / m ² using a high-pressure mercury lamp without a photomask. Thereafter, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was sprayed onto these substrates at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm), and spray development was performed for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230 ° C. for 30 minutes, thereby forming a colored hardened film on the substrate. This was used as a substrate (T-1).

Next, a spin coater was used to coat the substrate (T-1) containing the polyorganosiloxane, trimellitic anhydride, 2-ethyl-4-methylimidazole, and propylene glycol obtained according to Example 1 of the specification of Japanese Patent No. 4697423. A resin composition for forming a protective film of monomethyl ether acetate. Thereafter, pre-baking was performed on a hot plate at 90 ° C. for 5 minutes and further baked in a clean oven at 230 ° C. for 30 minutes, thereby forming a protective film having a thickness of 2.0 μm on the upper surface of the colored cured film. The obtained substrate was used as a substrate (T-2).

The contrast of the substrate (T-1) and the substrate (T-2) was measured by the same method as described above, and the contrast change rate was determined from the following formula. As a result, a case where the contrast change rate was less than 15% was evaluated as “○”, a case where 15% or more and less than 30% was evaluated as “Δ”, and a case where 30% or more was evaluated as “×”. The evaluation results are shown in Table 3. In addition, it can be said that the smaller the contrast change rate, the better.

Contrast change rate = ((contrast of substrate (T-2))-(contrast of substrate (T-1))) × 100 / (contrast of substrate (T-1))

Examples 2 to 11 and Comparative Examples 1 to 6

In Example 1, the coloring compositions (S-2) to (S-17) were prepared in the same manner as in Example 1 except that the kinds and amounts of the components were changed as shown in Table 3. Next, evaluation was performed in the same manner as in Example 1 except that the coloring composition (S-2) to (S-17) were used instead of the coloring composition (S-1). The results are shown in Table 3.

In Table 3, "α / β" represents the molar ratio of the fluorescent-emitting portion in the compound group α to the fluorescent-absorbing portion in the compound group β.

Claims (14)

A coloring composition comprising (A) a coloring agent and (B) a polymerizable compound, wherein (A) the coloring agent comprises a combination of (i) or (ii): (i) a polymer ( α4) Combination with monomer (β3) (ii) Combination of monomer (α3) and polymer (β4) This monomer (α3) has At least one of a chromophore and a cyanine chromophore and a polymerizable group, the polymer (α4) contains the monomer (α3) as a structural unit, and the monomer (β3) has a group selected from triaryl At least one of a methanophore and anthraquinone chromophore and a polymerizable group, the polymer (β4) contains the monomer (β3) as a structural unit. The coloring composition according to claim 1, wherein the monomer (β3) is an ethylenically unsaturated monomer having at least one chromophore selected from a triarylmethane chromophore and an anthraquinone chromophore. The coloring composition according to claim 1, wherein the monomer (α3) is An ethylenically unsaturated monomer of at least one of a chromophore and a cyanine chromophore. For example, the colored composition of claim 1, wherein the monomer (α3) is a monomer represented by formula (1-1), and the monomer (β3) is a monomer represented by formula (1-2), [In the formula (1-1), R ¹ each independently represents a hydrogen atom or a methyl group; X ¹ each independently represents a directly-bonded, substituted or unsubstituted divalent hydrocarbon group, or the divalent hydrocarbon group and one or more A divalent group composed of a linking group containing atoms other than carbon and hydrogen atoms; P represents Chromophore or cyanine chromophore; g represents an integer of 1 or more]; [In the formula (1-2), R ² represents a hydrogen atom or a methyl group; X ² represents a directly-bonded, substituted or unsubstituted divalent hydrocarbon group, or the divalent hydrocarbon group and one or more containing carbon atoms and A divalent group composed of a combination of linking groups of atoms other than a hydrogen atom; Q represents a triarylmethane chromophore or anthraquinone chromophore; h represents an integer of 1 or more]. The colored composition according to claim 1, wherein the polymer (α4) and the polymer (β4) have copolymerizable ethylenically unsaturated monomers other than the monomer (α3) and the monomer (β3), respectively. As a structural unit, the other copolymerizable ethylenically unsaturated monomer includes a (meth) acrylate. The coloring composition according to claim 1, wherein the content ratio of the combination of the polymer (α4) and the monomer (β3) or the combination of the monomer (α3) and the polymer (β4) is a molar ratio. It is counted as 99/1 ~ 40/60. A coloring composition comprising (A) a colorant and (B) a polymerizable compound, wherein (A) the colorant comprises a combination of the following (iii) or (iv): (iii) a polymer (α2) and a monomer Combination (iv1) of monomer (β1) and combination of monomer (α1) and polymer (β2) This monomer (α1) has a fluorescent emitting site and a polymerizable group, and this polymer (α2) contains the monomer (α1) as a structural unit, the monomer (β1) has a site that absorbs the fluorescence and a polymerizable group, and the polymer (β2) contains the monomer (β1) as a structural unit. The colored composition according to claim 7, wherein the monomer (α1) is a monomer represented by the formula (1-1), and the monomer (β1) is a monomer represented by the formula (1-2), [In the formula (1-1), R ¹ each independently represents a hydrogen atom or a methyl group; X ¹ each independently represents a directly-bonded, substituted or unsubstituted divalent hydrocarbon group, or the divalent hydrocarbon group and one or more A divalent group consisting of a combination of a linking group containing atoms other than carbon and hydrogen atoms; P represents a site emitting fluorescence; g represents an integer of 1 or more]; [In the formula (1-2), R ² represents a hydrogen atom or a methyl group; X ² represents a directly-bonded, substituted or unsubstituted divalent hydrocarbon group, or the divalent hydrocarbon group and one or more containing carbon atoms and A divalent group composed of a combination of linking groups of atoms other than a hydrogen atom; Q represents a site that absorbs fluorescence; h represents an integer of 1 or more]. The colored composition according to claim 7, wherein the polymer (α2) and the polymer (β2) have copolymerizable ethylenically unsaturated monomers other than the monomer (α1) and the monomer (β1), respectively. As a structural unit, the other copolymerizable ethylenically unsaturated monomer includes a (meth) acrylate. The colored composition according to claim 7, wherein the content ratio of the combination of the polymer (α2) and the monomer (β1), or the combination of the monomer (α1) and the polymer (β2) is a molar ratio. It is counted as 99/1 ~ 40/60. The coloring composition according to any one of claims 1 to 10, further comprising (C) a binder resin. The coloring composition according to any one of claims 1 to 10, further comprising a photopolymerization initiator, the photopolymerization initiator including an O-fluorenyl oxime-based compound. A colored hardened film is formed using the colored composition according to any one of claims 1 to 12. A display element having a colored hardened film as claimed in claim 13.