JP2017066377A - Coloring composition, colored cured film, display element and solid state image sensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition suitable for forming a colored cured film capable of achieving high heat resistance, solvent resistance and good voltage retention.SOLUTION: There is provided a coloring composition containing (A) a coloring agent, (B) a binder resin and (C) a polymerizable compound, wherein the (A) coloring agent contains a salt of a cationic cyanine chromophoric group and imide anion having a polymerizable unsaturated group. The imide anion having the polymerizable unsaturated group is preferably an anion represented by the following formula (3), where Yrepresents a group having a polymerizable unsaturated group and Yrepresents a halo group, a halogenated hydrocarbon group, a heteroaryl group or a group by combining a connecting group containing a carbon atom, a hydrogen atom or an atom other than halogen atoms, a halogen substituted alkanediyl group and a monovalent group selected from an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or a substituted or unsubstituted aryl group.SELECTED DRAWING: None

Description

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

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

  By the way, a color filter using a pigment as a colorant tends to cause a decrease in luminance, contrast, and the like of a display element due to light scattering by pigment particles. Therefore, a technique using a dye instead of a pigment as a colorant has been proposed (see, for example, Patent Document 1). However, since the dye has a fragile pigment skeleton, the heat resistance and the solvent resistance are remarkably insufficient, so that there are many problems as a coloring composition for a color filter and it is difficult to put it to practical use. Among these, cyanine dyes are greatly deficient in heat resistance because the azo bond that is the chromophore is weak against heat.

As a method for improving the heat resistance of the cyanine dye, various anions of low molecular weight (Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , OH ⁻ , carboxylate anion, sulfonate anion, It has been proposed to use a salt containing a borate anion and a monovalent organometallic complex anion as a colorant for a color filter (see, for example, Patent Documents 2 to 3). However, even if a color filter is produced using these dyes, not only the heat resistance is insufficient, but also the precipitation of foreign matters is observed on the color filter substrate due to the low solubility of the organic solvent. There are many problems such as causing a decrease in brightness, and it has not been put into practical use. Therefore, a salt-forming compound obtained by reacting an imidoanion anion with a cationic cyanine dye for the purpose of providing a color filter which is excellent in lightness, heat resistance and contrast ratio and does not generate foreign matter on the coating film. The coloring composition for color filters containing this is proposed (refer patent document 4). However, the inventors have found that a color filter formed using the colored composition has a deteriorated voltage holding ratio.

JP-A-6-075375 JP 2008-242324 A JP 2009-235392 A Japanese Patent Laying-Open No. 2015-118267

  The subject of this invention is providing the coloring composition suitable for formation of the colored cured film which can make high heat resistance, solvent resistance, and a favorable voltage holding ratio compatible. Furthermore, the subject of this invention is providing the display element and solid-state image sensor which comprise the colored cured film formed using the said colored composition, and the said colored cured film.

  The present inventors have conducted extensive research in view of such circumstances, and as a colorant, can solve the above problems by using a salt of a cationic cyanine chromophore and an imide anion having a polymerizable unsaturated group. The present inventors have found that this can be done and have completed the present invention.

  That is, the present invention is a colored composition comprising (A) a colorant, (B) a binder resin, and (C) a polymerizable compound, wherein (A) the colorant comprises a cationic cyanine chromophore and a polymerizable unsaturated group. The present invention provides a coloring composition comprising a salt with an imide anion having a group (hereinafter also referred to as “specific colorant”).

  If the coloring composition of this invention is used, the colored cured film which can make high heat resistance and solvent resistance compatible with a favorable voltage retention can be formed. Therefore, the colored composition of the present invention can be used very suitably for the production of solid-state imaging devices such as color liquid crystal display devices, organic EL display devices, display devices such as electronic paper, and CMOS image sensors.

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

-(A) Colorant-
The coloring composition of the present invention contains a specific colorant. First, the cationic cyanine chromophore constituting the specific colorant will be described.

  Examples of the cationic cyanine chromophore of the present invention include a structure represented by the following formula (1).

[In Formula (1),
Ring Z ¹ and Ring Z ² each independently represent a substituted or unsubstituted heterocycle,
p represents 1 or 2, provided that when p is 2, a plurality of R ¹ and R ² may be the same or different;
R ^{1 to} R ³ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group. ]

The heterocyclic ring in ring Z ¹ and ring Z ² may be a monocyclic heterocyclic ring or a polycyclic heterocyclic ring. The heterocyclic ring may be an unsaturated ring or a saturated ring, and may have two or more hetero atoms (for example, a nitrogen atom, an oxygen atom, and a sulfur atom) of the same type or different types in the ring. For example, nitrogen-containing alicyclic heterocycles such as pyrrolidine ring, pyrazoline ring, morpholine ring, thiomorpholine ring, piperidine ring, piperazine ring, homopiperazine ring, tetrahydropyrimidine ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, Quinoline ring, isoquinoline ring, phthalazine ring, quinoxaline ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, benzothiazole ring, oxazole ring, indole ring, indazole ring, benzimidazole ring, benzoxazole, phthalimide ring, etc. And other aromatic heterocycles such as a nitrogen-containing aromatic heterocycle, thienyl ring, furan ring, and purine ring. Among these, a nitrogen-containing aromatic heterocyclic ring is preferable, an indole ring, a benzoxazole ring, and a benzothiazole ring are more preferable, and an indole ring is still more preferable.

p represents 1 or 2, and p is preferably 1.
Examples of the halogen atom in R ^{1 to} R ³ include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the hydrocarbon group in R ^{1 to} R ³ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Here, in the present specification, the “alicyclic hydrocarbon group” is a concept excluding an aliphatic hydrocarbon group having no cyclic structure.

  The aliphatic hydrocarbon group may be saturated or unsaturated, and examples thereof include an alkyl group, an alkenyl group, and an alkynyl group. Carbon number of an aliphatic hydrocarbon group becomes like this. Preferably it is 1-30, More preferably, it is 1-20, More preferably, it is 1-12. These aliphatic hydrocarbon groups may be linear or branched. Specific examples of the alkyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, and nonyl. Group, decyl group, undecyl group, 1-methyldecyl group, dodecyl group, 1-methylundecyl group, 1-ethyldecyl group, tridecyl group, tetradecyl group, tert-dodecyl group, pentadecyl group, 1-heptyloctyl group, hexadecyl group And octadecyl group. Specific examples of the alkenyl group include, for example, ethenyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1,3-butadienyl group, 1-pentenyl group, 2-pentenyl group, A 1-hexenyl group, 2-ethyl-2-butenyl group, 2-octenyl group, (4-ethenyl) -5-hexenyl group, 2-decenyl group and the like can be mentioned. Specific examples of the alkynyl group include, for example, ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-ethyl-2-butynyl group, 2 -Octynyl group, (4-ethynyl) -5-hexynyl group, 2-decynyl group and the like can be mentioned.

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

  Examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10. Here, in the present specification, the “aryl group” refers to a monocyclic to tricyclic aromatic hydrocarbon group, and specific examples thereof include, for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenylene group. , An azulenyl group, a 9-fluorenyl group, and the like. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a trityl group.

Examples of the substituent for the heterocyclic ring in ring Z ¹ and ring Z ² and the hydrocarbon group in R ^{1 to} R ³ include a halogen atom, a hydroxyl group, a cyano group, a formyl group, a carboxy group, a nitro group, an amino group, and a dialkylamino group. Group, diarylamino group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylthio group, arylthio group, trialkylsilyl group, mercapto group, allyl group, alkylsulfonyl group, alkylsulfamoyl group, aliphatic hydrocarbon group, A heterocyclic group, an aromatic hydrocarbon group, etc. can be mentioned. These substituents may further have a substituent.

  The structure represented by the formula (1) is preferably a structure represented by the following formula (2).

[In Formula (2),
R ^{1 to} R ³ are as defined above.
Ring Z ^1A and ring Z ^2A each independently represent a substituted or unsubstituted aromatic hydrocarbon ring.
T ¹ and T ² each independently represent —O—, —S—, or —CR ⁶ R ⁷ —.
R ^{4 to} R ⁷ each independently represent a substituted or unsubstituted hydrocarbon group. ]

The aromatic hydrocarbon ring in ring Z ^1A and ring Z ^2A is preferably one having 6 to 20 carbon atoms, more preferably one having 6 to 10 carbon atoms, and particularly preferably a benzene ring.

As R < ¹ > -R < ³ >, a hydrogen atom is preferable.
T ¹ and T ² are preferably —O— or —CR ⁶ R ⁷ —. As the hydrocarbon group for R ⁶ and R ⁷ , an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable. As an alkyl group, a C1-C8 alkyl group is preferable, a C1-C4 alkyl group is more preferable, and a methyl group and an ethyl group are especially preferable.

Examples of the hydrocarbon group in R ⁴ and R ⁵ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples thereof include the same ones as exemplified for the hydrocarbon group for R ¹ to R ^3. Of these, the hydrocarbon group for R ⁴ and R ^5, preferably aliphatic hydrocarbon group, an alkyl group is more preferable. 1-12 are preferable, as for carbon number of an alkyl group, 1-8 are more preferable, and 1-6 are especially preferable.

Examples of the aromatic hydrocarbon ring related to ring Z ^1A and ring Z ^2A and the substituent of the hydrocarbon group related to R ^{4 to} R ⁷ include the same ones as described above.

  The structure represented by Formula (1) and the structure represented by Formula (2) are electrically cationic. Although the valence is not specifically limited, 1-3 valence is preferable and monovalence is more preferable. The specific colorant has a counter anion so as to be electrically neutral. When the structure represented by the formula (1) and the structure represented by the formula (2) are divalent or more, the pair Anions other than imide anions having a polymerizable unsaturated group (for example, halide ions, hydroxide ions, monovalent organometallic complex anions, cyanide ions, nitrate ions, perchlorate ions, acetate ions, carvone ions) Monovalent anions such as acid anions, sulfonic acid anions, boron anions, imide anions and methide anions having no polymerizable unsaturated group; divalent anions such as sulfate ions and carbonate ions; trivalent anions such as phosphate ions ) May be included. For example, when the structure represented by the formula (1) and the structure represented by the formula (2) are divalent cationic cyanine chromophores, the chromophore is a monovalent imide having a polymerizable unsaturated group. Two anions may be included, or a monovalent imide anion having a polymerizable unsaturated group and a monovalent tetrakis (pentafluorophenyl) borate may be included.

  Specific examples of such cationic cyanine chromophores include, for example, the chromophores described in the following compound groups a to d, and the color development described in paragraphs [0044] to [0053] of JP-A-2015-118267. A group can be exemplified.

Next, the imide anion having a polymerizable unsaturated group constituting the specific colorant will be described.
The imide anion having a polymerizable unsaturated group is usually a monovalent anion, and examples thereof include an anion represented by the following formula (3).

[In Formula (3),
Y ¹ represents a group having a polymerizable unsaturated group,
Y ² is a halo group, a halogenated hydrocarbon group, a linking group containing a carbon atom, a hydrogen atom or an atom other than a halogen atom, a halogen-substituted alkanediyl group, an alkyl group, an alicyclic hydrocarbon group, a heteroaryl A group formed by combining a group and a monovalent group selected from a substituted or unsubstituted aryl group; ]

Examples of the halo group for Y ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group in Y ² include (1) an aliphatic hydrocarbon group, (2) an alicyclic hydrocarbon group, and (3) an alicyclic hydrocarbon as a substituent. Group having an aliphatic hydrocarbon group (hereinafter referred to as “alicyclic hydrocarbon-substituted aliphatic hydrocarbon group”), (4) an aromatic hydrocarbon group, and (5) an aliphatic hydrocarbon group as a substituent. Aromatic hydrocarbon group (hereinafter referred to as “aliphatic hydrocarbon-substituted aromatic hydrocarbon group”), (6) aliphatic hydrocarbon group having an aromatic hydrocarbon group as a substituent (hereinafter referred to as “aromatic hydrocarbon”). And a substituted aliphatic hydrocarbon group ”. The hydrocarbon group constituting the skeleton of Y ² is preferably the following characteristic group from the viewpoint of solubility in an organic solvent.

That is, the (1) aliphatic hydrocarbon group is preferably an alkyl group, and the number of carbon atoms thereof is preferably 1-20, and particularly preferably 1-8. Specifically, the same thing as the above-mentioned can be mentioned.
The (2) alicyclic hydrocarbon group may be a 2- to 4-ring bridged alicyclic hydrocarbon group. The alicyclic hydrocarbon group is preferably an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. Specifically, the same thing as the above-mentioned can be mentioned, for example.
The (3) alicyclic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an alicyclic saturated hydrocarbon-substituted alkyl group, and the total carbon number is preferably 4 to 20, particularly 6 to 14 It is preferable that Specific examples include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclohexylmethyl group, a cyclohexylpropyl group, an adamantylmethyl group, a 1- (1-adamantyl) ethyl group, and a cyclopentylethyl group.
The (4) aromatic hydrocarbon group is preferably an aryl group having 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. Specific examples thereof include those described above, and among them, a phenyl group is preferable.
The (5) aliphatic hydrocarbon-substituted aromatic hydrocarbon group is preferably an alkyl-substituted phenyl group, and the total carbon number thereof is preferably 7 to 30, and particularly preferably 7 to 20. Specifically, a tolyl group, a xylyl group, a mesityl group, etc. can be mentioned, for example.
The (6) aromatic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an aralkyl group, and the total carbon number thereof is preferably 7 to 30, and particularly preferably 7 to 20. Specifically, the same thing as the above-mentioned can be mentioned.

  Among these, the hydrocarbon group forming the skeleton of the halogenated hydrocarbon group includes (1) an aliphatic hydrocarbon group, (3) an alicyclic hydrocarbon-substituted aliphatic hydrocarbon group, and (4) an aromatic hydrocarbon. Group, (5) aliphatic hydrocarbon-substituted aromatic hydrocarbon group or (6) aromatic hydrocarbon-substituted aliphatic hydrocarbon group, alkyl group, alicyclic saturated hydrocarbon-substituted alkyl group, phenyl group, alkyl-substituted group A phenyl group and an aralkyl group are more preferable, and an alkyl group is particularly preferable.

In Y ² , the halogen atom in the halogenated hydrocarbon group is preferably a fluorine atom from the viewpoint of heat resistance of the colorant, and the fluorine atom substitutes a part or all of the hydrogen atoms of the hydrocarbon group. May be. By selecting a fluorine atom as a substituent, the anion portion of the colorant becomes a conjugate base of an organic acid having a higher acidity, so that a salt with a stronger ionic bond is formed and heat resistance is increased. Conceivable.

Y ² includes a linking group containing a carbon atom, a hydrogen atom or an atom other than a halogen atom, a halogen-substituted alkanediyl group, an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group, and a substituted or unsubstituted aryl group. A group formed by combining a selected monovalent group may be used. Examples of the linking group containing an atom other than a carbon atom, a hydrogen atom and a halogen atom include —O—, —S—, —CO—, —COO—, —CONH—, —SO ₂ — and the like. In addition, examples of the halogen-substituted alkanediyl group include groups in which some or all of the hydrogen atoms of the alkanediyl group have been substituted with halogen atoms. As the alkanediyl group, an alkanediyl group having a linear or branched chain having 1 to 10 carbon atoms is preferable, and specifically, a methylene group, an ethylene group, an ethane-1,1-diyl group, propane-1,1. -Diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane -1,4-diyl group, pentane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, octane-1,8- A diyl group, a decane-1,10-diyl group, etc. are mentioned. Among these, an alkanediyl group having 2 to 8 carbon atoms is preferable, and an alkanediyl group having 2 to 6 carbon atoms is more preferable. The halogen atom substituted for the alkanediyl group is preferably a fluorine atom from the viewpoint of heat resistance. Further, the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably 1 to 8 carbon atoms. Specific examples include the same ones as described above. Moreover, as a cycloaliphatic hydrocarbon group, a 2-4 ring bridged cycloaliphatic hydrocarbon group may be sufficient, and a C3-C20, Furthermore, C3-C12 alicyclic saturated hydrocarbon group is preferable. Specific examples include the same ones as described above. The heteroaryl group is preferably a group composed of a 5- to 10-membered aromatic heterocycle containing one or more heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom. Specific examples include a furyl group, a thienyl group, a pyrrolyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, and a carbazolyl group. The aryl group is preferably an aryl group having 6 to 14 carbon atoms and more preferably 6 to 10 carbon atoms, particularly preferably a phenyl group or a naphthyl group. In addition, as a substituent of an aryl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a halogen atom, or a trifluoromethyl group is mentioned, for example. Specific examples of the alkyl group having 1 to 6 carbon atoms and the halogen atom are the same as those described above. Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, sec-butoxy group, and n-pentyloxy group. , Iso-pentyloxy group, n-hexyloxy group, methoxymethoxy group, ethoxyethoxy group and the like. In addition, the position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different.

In the present invention, from the viewpoint of the heat resistance of the colorant, Y ² includes a halogenated hydrocarbon group or a linking group containing a carbon atom, a hydrogen atom or an atom other than a halogen atom, a halogen-substituted alkanediyl group, and an alkyl. A group formed by combining a monovalent group selected from a group, an alicyclic hydrocarbon group, a heteroaryl group, and a substituted or unsubstituted aryl group is preferred. In the following formula (4-1) or (4-2) The group represented by the following formula (4-1) which forms the conjugate base of the organic acid with a stronger acidity is more preferable.

[In Formula (4-1),
R ¹⁷ is a hydrogen atom, a fluorine atom, an alkyl group, fluorinated alkyl group, an alicyclic hydrocarbon group, an alkoxy group, fluorinated alkoxy ^group, R 18 COOR ¹⁹ - indicates or ^R 20 ^COOR 21 -CFH-,
R ¹⁸ and R ²⁰ each independently represent an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group, or a substituted or unsubstituted aryl group;
R ¹⁹ and R ²¹ each independently represent an alkanediyl group,
n represents an integer of 1 or more,
“*” Indicates a bond. ]

[In Formula (4-2),
R ^{12 to} R ¹⁶ each independently represent a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluorinated alkyl group or an alkoxy group,
“*” Indicates a bond.
However, at least one of R ^{12 to} R ¹⁶ is a fluorine atom or a fluorinated alkyl group. ]

In formula (4-1), the alkyl group for R ¹⁷ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and further 1 to 4 carbon atoms. Specific examples include the same ones as described above. The fluorinated alkyl group for R ¹⁷ is preferably a fluorinated alkyl group having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and further 1 to 4 carbon atoms. Specific examples include those obtained by substituting some or all of the hydrogen atoms of the aforementioned alkyl groups with fluorine atoms, and perfluoroalkyl groups are particularly preferred.
The alicyclic hydrocarbon group for R ¹⁷ may be a 2-4 ring bridged alicyclic hydrocarbon group. The alicyclic hydrocarbon group is preferably an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. Specific examples include the same ones as described above.
The alkoxy group for R ¹⁷ is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and further 1 to 4 carbon atoms. Specific examples include the same as described above and a 3- (iso-propyloxy) propyloxy group. Further, the fluorinated alkoxy group for R ¹⁷ is preferably a fluorinated alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and further 1 to 4 carbon atoms. Specific examples include those in which part or all of the hydrogen atoms of the aforementioned alkoxy group are substituted with fluorine atoms.

In R ¹⁸ COOR ¹⁹ —, R ²⁰ COOR ²¹ CFH— in R ¹⁷ , R ¹⁸ and R ²⁰ are each independently an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group, or a substituted or unsubstituted aryl group. However, 1-12 are preferable and, as for carbon number of an alkyl group, 1-8 are more preferable. Specific examples include the same ones as described above. The alicyclic hydrocarbon group may be a 2-4 ring bridged alicyclic hydrocarbon group, and is preferably an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. Specific examples include the same ones as described above. The heteroaryl group is preferably a group composed of a 5- to 10-membered aromatic heterocycle containing one or more heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom. Specific examples include a furyl group, a thienyl group, a pyrrolyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, and a carbazolyl group. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably a phenyl group. In addition, as a substituent of an aryl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a halogen atom, or a trifluoromethyl group is mentioned, for example, As a specific example, it is the same as the above-mentioned Things can be mentioned. In addition, the position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different.
^{Also, R 19} and ^{R 21} are independently of each other, show alkanediyl group, preferably alkanediyl group having 1 to 6 carbon atoms. Specific examples include the same ones as described above. Among these, an ethylene group is preferable from the viewpoint of ease of production.

In addition, 10 is preferable and the upper limit of n is more preferable.
R ¹⁷ is preferably a fluorine atom, a fluorinated alkyl group, an alicyclic hydrocarbon group, a fluorinated alkoxy group, R ¹⁸ COOR ¹⁹ -or R ²⁰ COOR ²¹ CFH-, and particularly preferably a fluorine atom or an alicyclic hydrocarbon group. , A perfluoroalkoxy group, R ¹⁸ COOCH ₂ CH ₂ — or R ²⁰ COOCH ₂ CH ₂ CFH— is preferable.
In the formula (4-2), examples of the alkyl group, the fluorinated alkyl group, and the alkoxy group in R ^{12 to} R ¹⁶ include an alkyl group, a fluorinated alkyl group, and an alkoxy group in R ¹⁷ of the formula (4-1). A configuration similar to that of the base can be employed. However, at least one of R ^{12 to} R ¹⁶ is a fluorine atom or a fluorinated alkyl group, but at least three of R ^{12 to} R ¹⁶ are preferably a fluorine atom or a fluorinated alkyl group.

Y ¹ is not particularly limited, but an organic group having a polymerizable unsaturated group is preferable. Examples of the organic group include a chain organic group and a cyclic organic group, and the bonding position and the number of bonds of the polymerizable unsaturated group with respect to these organic groups are arbitrary. In addition, when the organic group has a substituent other than the polymerizable unsaturated group, the type, bond position, and bond number are not particularly limited.

Among these, Y ¹ is preferably a group represented by the following formula (5).

[In Formula (5),
L ¹ represents a single bond or a divalent organic group,
Q ¹ represents a polymerizable unsaturated group,
“* ¹ ” indicates a bond with N ⁻ . ]

Examples of the divalent organic group represented by L ¹ include a divalent hydrocarbon group, a divalent hydrocarbon group and a group formed by combining a linking group containing an atom other than a carbon atom and a hydrogen atom, or these And a group in which part of the hydrogen atoms in the group is substituted with a halogen atom. Examples of the divalent hydrocarbon group include an alkanediyl group, an arylene group, an arylenealkanediyl group, and the like. More specifically, as the divalent organic group, an alkanediyl group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, an arylene alkanediyl group having 7 to 20 carbon atoms, or 1 to 1 carbon atoms. At least one selected from 10 alkanediyl groups and arylene groups having 6 to 20 carbon atoms, and —O—, —S—, —COO—, —CONR ^a — (R ^a is a hydrogen atom or carbon atoms 1 to 8). And a group formed by combining at least one selected from —SO ₂ — and the like.

Specific examples of the alkanediyl group include an octane-1,8-diyl group, decane-1,10-diyl group, etc., in addition to the above-mentioned alkanediyl group having 1 to 6 carbon atoms. Among these, an alkanediyl group having 2 to 8 carbon atoms is preferable, and an alkanediyl group having 2 to 6 carbon atoms is more preferable.
Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, and an anthryl group. Among them, an arylene group having 6 to 10 carbon atoms is preferable, and a phenylene group is particularly preferable.
An arylene alkanediyl group is a divalent group formed by combining an arylene group and an alkanediyl group. As the arylenealkanediyl group, an arylenealkanediyl group having 7 to 15 carbon atoms is preferable, and an arylenealkanediyl group having 7 to 13 carbon atoms is more preferable from the viewpoint of availability of raw materials and production. Specific examples include phenylene C _1-6 alkanediyl groups such as a phenylenemethylene group, a phenylenedimethylene group, a phenylenetrimethylene group, a phenylenetetramethylene group, a phenylenepentamethylene group, and a phenylenehexamethylene group. The arylenealkanediyl group includes ortho, meta, and para isomers, and is preferably a para isomer from the viewpoint of less steric hindrance.

In addition, at least one selected from an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms, and -O-, -CO-, -S-, -COO-, -CONR ^a- (R ^a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) and at least one selected from —SO ₂ —, the alkanediyl group having 1 to 10 carbon atoms and the carbon number 6 may be used. and at least one selected from the arylene group ~20, -O -, - CO - , - COO- and -SO ₂ - comprising a combination of at least one group preferably selected from, 1 to 10 carbon atoms A group formed by combining at least one selected from an alkanediyl group and an arylene group having 6 to 20 carbon atoms and at least one selected from —CO— and —SO ₂ — is more preferable.

Y ¹ is more preferably a group represented by the following formula (6) from the viewpoint of heat resistance.

In [Equation ^(6), L 1, ^{Q 1} and ^{* 1} have the same meanings as defined above. ]

In Formula (6), L ¹ is an arylene group, an arylene alkanediyl group, at least one selected from an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms, and —O—. A group formed by combining is preferable. In addition, the suitable aspect of an arylene group and an arylene alkanediyl group is as having demonstrated above. Examples of the group formed by combining at least one selected from an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms with —O— include C _6-20 aryleneoxy C _1-6 alkanediyl. group is preferred, for _{example, C 6-20} arylene oxymethylene _{group, C 6-20} arylene-oxy dimethylene _{group, C 6-20} arylene oxy trimethylene _{group, C 6-20} arylene oxytetramethylene group, C _6-20 arylene Examples thereof include oxyheptamethylene group, C _{6-20 aryleneoxyhexamethylene} group, and more specifically, phenoxymethylene group, phenoxydimethylene group, phenoxytrimethylene group, phenoxytetramethylene group, phenoxyheptamethylene group, phenoxy. Phenoxy C _1-6 alkane such as hexamethylene group A diyl group can be mentioned.

  In the imide anion having a polymerizable unsaturated group, examples of the polymerizable unsaturated group include (meth) acryloyloxy group, vinylaryl group, allyl group and the like, and (meth) acryloyloxy from the viewpoint of voltage holding ratio. Group and vinylaryl group are more preferable.

  Specific examples of the imide anion having such a polymerizable unsaturated group include the anions described in the following compound group e.

  The specific colorant can be synthesized, for example, by mixing a solution containing a compound having a cationic cyanine chromophore and a solution containing a compound having an imide anion having a polymerizable unsaturated group.

  The coloring composition of this invention can also use another coloring agent together with a specific coloring agent as (A) coloring agent. Such other colorants can be used without any particular limitation, and colors and materials can be appropriately selected according to the use such as a color filter. Specific examples of the colorant include pigments and dyes other than the specific colorant, and these can be used alone or in combination of two or more.

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

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

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

  The colored composition of the present invention is suitable for forming a red colored cured film and a blue colored cured film, and particularly suitable for forming a blue colored cured film. When used for forming a red colored cured film, it is preferable to include a combination of a specific colorant and at least one selected from the group consisting of a red pigment, a xanthene dye, and a triarylmethane dye as another colorant. When used for forming a blue colored cured film, it may contain a combination of a specific colorant and at least one selected from the group consisting of a blue pigment, a xanthene dye, a triarylmethane dye and a dipyrromethene dye as another colorant. preferable. In these cases, the content ratio of the other colorants is preferably 30 to 99% by mass, more preferably 60 to 95% by mass with respect to the total colorants.

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

  The dye other than the specific colorant is not particularly limited. For example, in addition to the compounds classified as Dye in the color index (CI; issued by The Society of Dyers and Colorists), well-known Can be used.

  Such dyes include, for example, xanthene dyes, triarylmethane dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, quinophthalone dyes, coumarin dyes, pyrazolone dyes, quinoline dyes, nitro dyes, quinone imines from the structural aspect of chromophores. And dyes, phthalocyanine dyes, squarylium dyes, and the like.

  Moreover, in this invention, a well-known dispersing agent and dispersion | distribution adjuvant can also be included with the specific coloring agent and the other coloring agent mixed arbitrarily. Known dispersants include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. Dispersants, polyester dispersants, acrylic dispersants and the like can be mentioned, and examples of the dispersion aid include pigment derivatives.

  Such a dispersant can be obtained commercially. Examples of acrylic dispersants include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK Corporation (BYK)), and the like. Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (manufactured by Lubrizol Corp.) ), Etc., as polyethyleneimine dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), AJISPER PB880, Adisper PB881 (or more, Ajinomoto Fine-Techno Co., Ltd.) other like, can be mentioned BYK-LPN21324 (BYK Chemie (BYK) Co., Ltd.).

  Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivative of quinophthalone.

  (A) The content of the colorant is excellent in heat resistance and solvent resistance, and is usually a solid of a colored composition from the viewpoint of forming a colored cured film that can achieve both of these and a good voltage holding ratio at a high level. It is 5-70 mass% in a minute, Preferably it is 10-60 mass%. Here, solid content is components other than the solvent mentioned later.

-(B) Binder resin-
The binder resin of the present invention is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). And a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as “unsaturated monomer (b2)”). . Binder resin can be used 1 type or in mixture of 2 or more types.

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth). Examples thereof include acrylate and p-vinylbenzoic acid.
An unsaturated monomer (b1) can be used 1 type or in mixture of 2 or more types.

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

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

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

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

  Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.

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

The binder resin in the present invention has an Mw measured by GPC of usually 1,000 to 100,000, preferably 3,000 to 50,000. By adopting such an embodiment, the heat resistance and solvent resistance are further enhanced, and these and a good voltage holding ratio can be achieved at a high level, and the transferability and the generation of foreign substances can be effectively suppressed. Can do.
The Mw / Mn of the binder resin is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. Here, Mw and Mn are polystyrene-reduced number average molecular weights measured by GPC (elution solvent: tetrahydrofuran).

  The binder resin can be produced by a known method, for example, by a method disclosed in JP2003-222717A, JP2006-259680A, International Publication No. 2007/029871, etc. The structure, Mw, and Mw / Mn can also be controlled.

  In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts, More preferably, it is 50-200 mass parts. . By having such an aspect, not only can it form a colored cured film that is excellent in heat resistance and solvent resistance, and can achieve a high level of these and good voltage holding ratio, but also has excellent pattern shape, Furthermore, generation | occurrence | production of a deposit and a coating-film foreign material can be suppressed.

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

  Specific examples of the compound having two or more (meth) acryloyl groups include a reaction product (polyfunctional (meth) acrylate) of an aliphatic polyhydroxy compound and (meth) acrylic acid, a caprolactone-modified polyfunctional (meta ) Acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, reaction product of (meth) acrylate having hydroxyl group and polyfunctional isocyanate [polyfunctional urethane (meth) acrylate], hydroxyl group-containing (meth) acrylate and acid anhydride And a reaction product with a product [polyfunctional (meth) acrylate having a carboxyl group].

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and 3 such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of aliphatic polyhydroxy compounds having a valence higher than that. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol dihydrate. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

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

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

  Among these polymerizable compounds, a reaction product [polyfunctional (meth) acrylate] of trivalent or higher aliphatic polyhydroxy compound and (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylate, polyfunctional urethane (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N ′ -Tetra (alkoxymethyl) benzoguanamine is preferred. Among the reactants [polyfunctional (meth) acrylates] of trivalent or higher aliphatic polyhydroxy compounds and (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Among polyfunctional (meth) acrylates in which erythritol hexaacrylate has a carboxyl group, a reaction product of pentaerythritol triacrylate and succinic anhydride, a reaction product of dipentaerythritol pentaacrylate and succinic anhydride, It is particularly preferable because it has high strength, high heat resistance and solvent resistance, and good voltage holding ratio at a high level, is excellent in surface smoothness of the colored layer, and hardly generates foreign matter.

  The content of the polymerizable compound (C) in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 800 parts by mass, and 100 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. Is more preferable. By adopting such an aspect, high heat resistance and solvent resistance and good voltage holding ratio are compatible at a high level, and pixels with excellent pattern shape, or black matrix and black spacer with excellent light shielding properties are formed. can do.

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

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

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

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

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

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

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

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

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

  In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) polymeric compounds, and, as for content of a photoinitiator, 1-100 mass parts is still more preferable. By adopting such an embodiment, high heat resistance and solvent resistance, and good voltage holding ratio can be achieved at a high level, and not only the generation of foreign matter but also curability and film characteristics are improved. Can do.

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

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

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

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

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

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

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

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicone surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropro Adhesion promoters such as rutrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butane Such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. Examples include developability improvers.

Preparation Method of Colored Composition The colored composition of the present invention can be prepared by an appropriate method. Examples of the preparation method include (A) to (C), a solvent, and other optional additives. It can prepare by mixing with the component of. (A) When the colorant contains a pigment, the pigment is mixed and dispersed in a solvent in the presence of a dispersant, optionally with (B) a part of the binder resin, for example, using a bead mill, a roll mill or the like. Then, a pigment dispersion is prepared, and then, the specific colorant and the polymerizable compound (C), a photopolymerization initiator as necessary, an additional (B) binder resin, a solvent, and other components are added to the pigment dispersion. The method of preparing by adding and mixing is preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<Synthesis of specific colorant>
Synthesis example 1
A colorant (A-1) composed of a salt of a cationic cyanine chromophore represented by the following formula (cat-1) and an imide anion represented by the following formula (ani-1) was synthesized. The colorant (A-1) corresponds to a specific colorant.

Synthesis Examples 2-18
In Synthesis Example 1, coloring agents (A-2) to (A-18) were synthesized by changing the types of cationic cyanine chromophore and imide anion as shown in Table 1. Colorants (A-2) to (A-12) correspond to specific colorants, and colorants (A-13) to (A-18) do not correspond to specific colorants.

  In Table 1, “TFSI” represents a bis (trifluoromethanesulfonyl) imide anion, and “Cl” represents a chloride ion.

cat-1: Compound (C1-2-1) described in JP-A No. 2015-049482
cat-2: cyanine dye A-1 described in Chemical formula 20 of JP-A-2015-118267
cat-3: Compound (C1-3-1) described in JP-A-2015-049482
cat-4: cyanine dye A-2 described in Chemical formula 21 of JP-A-2015-118267
cat-5: Compound cat-6 described in Chemical Formula 4 of JP-A-2015-004014: Compound cat-7 described in Chemical Formula 16 of JP-A-2015-004014: JP-A-2014-224970 The compound represented by the formula (F-5) described in the publication

ani-4: Compound ani-5 described in Chemical Formula 38 of JP2013-163804A: Compound ani-6 described in Chemical Formula 40 of JP2013-163804A: International Publication No. 2007/091817 Compound ani-7 described in Example 1 of the pamphlet No. pamphlet: Compound ani-8 described in chemical formula 51 of JP-A-2015-118267: described in chemical formula 72 of JP-A-2015-118267 Compound ani-9: Compound described in Chemical formula 71 of JP-A-2015-118267

<Preparation of colorant solution>
Preparation Example 1
A colorant solution (1) was prepared by mixing 10 parts by weight of the colorant (A-1) and 90 parts by weight of diacetone alcohol.

Preparation Examples 2-18
In Preparation Example 1, colorant solutions (2) to (18) were prepared in the same manner as Preparation Example 1, except that the colorants (A-2) to (A-18) were used instead of the colorant (A-1). ) Was prepared.

<Preparation of pigment dispersion>
Preparation Example 19
15 parts by mass of a pigment having a structure represented by the following formula, BYK-LPN21116 (manufactured by BYK Corporation) (solid content concentration 40% by mass) 12.5 parts by mass as a dispersant, propylene glycol monomethyl ether acetate as a solvent Using 72.5 parts by mass, a pigment dispersion (a-1) was prepared by treatment with a bead mill.

<Synthesis of binder resin>
Synthesis Example 19
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate 23 parts by mass, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) The solution was added dropwise over a period of time and polymerized for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The obtained binder resin had Mw of 12,200 and Mn of 6,500. This binder resin is referred to as “binder resin (B-1)”.

<Preparation and evaluation of coloring composition>
Example 1
(A) 21.3 parts by mass of the pigment dispersion (a-1) as a colorant and 6.0 parts by mass of the colorant solution (1), (B) 12.4 parts by mass of the binder resin (B-1) solution as a binder resin Parts (solid content concentration 33% by mass), (C) M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Toagosei Co., Ltd. as a polymerizable compound, 8.2 parts by mass, photopolymerization initiator As 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name: IRGACURE 369, manufactured by Ciba Specialty Chemicals) and NCI-930 (trade name) (Made by ADEKA) 0.1 mass part, 10 mass% propylene glycol monomethyl ether solution of chromium complex compound represented by the following formula 0.0 part by mass, 0.02 part by mass of Megafac F-554 (manufactured by DIC Corporation) as a fluorosurfactant, and propylene glycol monomethyl ether acetate as a solvent, and a solid composition having a solid content concentration of 20% by mass (CR1) was prepared.

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

Evaluation of solvent resistance The colored composition (CR1) was applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed using a spin coater, and then heated on a 90 ° C. hot plate. Pre-baking was performed for 2 minutes to form a coating film having a thickness of 2.5 μm. Subsequently, after cooling this board | substrate to room temperature, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed to the coating film through the photomask using the high pressure mercury lamp with the exposure amount of 400 J / m < ² >. Then, shower development was performed for 90 seconds by discharging the developing solution which consists of 0.04 mass% potassium hydroxide aqueous solution of 23 degreeC with respect to this board | substrate with the developing pressure of 1 kgf / cm < ² > (nozzle diameter of 1 mm). Thereafter, this substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 30 minutes to form a dot pattern on the substrate. About the obtained dot pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), a C light source, a chromaticity coordinate value (x, y) and a stimulus value (Y) in the CIE color system with a 2-degree field of view. Was measured.
Next, the substrate was immersed in propylene glycol monomethyl ether acetate at 80 ° C. for 40 minutes. About the dot pattern after immersion, chromaticity coordinate value (x, y) and stimulus value (Y) were measured in the same manner as described above. Then, the color change before and after immersion, that is, ΔE ^* _ab was obtained.
As a result, the case where the value of ΔE ^* _ab was less than 3.0 was evaluated as “◯”, the case of 3.0 or more and less than 5.0 was evaluated as “Δ”, and the case of 5.0 or more was evaluated as “x”. The evaluation results are shown in Table 2. It can be said that the smaller the ΔE ^* _ab value, the better the solvent resistance.

Evaluation of voltage holding ratio A SiO ₂ film for preventing elution of sodium ions was formed on the surface, and an obtained ITO (indium-tin oxide alloy) electrode was deposited on a soda glass substrate in a predetermined shape. CR1) was spin-coated and then pre-baked on a hot plate at 100 ° C. for 1 minute to form a film having a thickness of 2.0 μm. Subsequently, the coating was exposed at an exposure amount of 700 J / m ² without using a photomask. Thereafter, the substrate was developed by being immersed in a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, washed with ultrapure water, and air-dried. Further, post-baking was performed at 230 ° C. for 30 minutes to cure the coating film to form a cured film.
Next, the substrate on which the cured film is formed and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealing agent mixed with 1.8 mm glass beads, and then Merck liquid crystal (MLC6608) is injected. Thus, a liquid crystal cell was produced. Next, the liquid crystal cell was placed in a constant temperature bath at 60 ° C., and the voltage holding ratio (%) of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system (VHR-1A type, Toyo Technica Co., Ltd.). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. As a result, the case where the value of the voltage holding ratio was 90% or more was evaluated as “◯”, the case where it was 80% or more and less than 90% was evaluated as “Δ”, and the case where it was less than 80% was evaluated as “X”. Here, the voltage holding ratio is a value determined by (liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds). The results are shown in Table 2.

Examples 2-12 and Comparative Examples 1-6
Colored compositions (CR2) to (CR18) were prepared in the same manner as in Example 1 except that the colorant solutions (2) to (18) were used in place of the colorant solution (1). Subsequently, heat resistance, solvent resistance, and voltage holding ratio were evaluated in the same manner as in Example 1 except that the colored compositions (CR2) to (CR18) were used instead of the colored composition (CR1). The results are shown in Table 2.

Claims (8)

A coloring composition comprising (A) a colorant, (B) a binder resin and (C) a polymerizable compound,
(A) A colored composition, wherein the colorant comprises a salt of a cationic cyanine chromophore and an imide anion having a polymerizable unsaturated group. The coloring composition of Claim 1 whose imide anion which has a polymerizable unsaturated group is an anion represented by following formula (3).

[In Formula (3),
Y ¹ represents a group having a polymerizable unsaturated group,
Y ² is a halo group, a halogenated hydrocarbon group, a linking group containing a carbon atom, a hydrogen atom or an atom other than a halogen atom, a halogen-substituted alkanediyl group, an alkyl group, an alicyclic hydrocarbon group, a heteroaryl A group formed by combining a group and a monovalent group selected from a substituted or unsubstituted aryl group; ] The coloring composition according to claim 2, wherein Y ¹ is a group represented by the following formula (5).

[In Formula (5),
L ¹ represents a single bond or a divalent organic group,
Q ¹ represents a polymerizable unsaturated group,
“* ¹ ” indicates a bond with N ⁻ . ]   The coloring composition according to any one of claims 1 to 3, wherein the polymerizable unsaturated group is a (meth) acryloyloxy group, a vinylaryl group or an allyl group. The colored composition according to any one of claims 1 to 4, wherein the cationic cyanine chromophore has a structure represented by the following formula (1).

[In Formula (1),
Ring Z ¹ and Ring Z ² each independently represent a substituted or unsubstituted heterocycle,
p represents 1 or 2, provided that when p is 2, a plurality of R ¹ and R ² may be the same or different;
R ^{1 to} R ³ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group. ]   A colored cured film comprising a salt of a cationic cyanine chromophore and an imide anion having a polymerizable unsaturated group.   A display element comprising the colored cured film according to claim 6.   A solid-state imaging device comprising the colored cured film according to claim 6.