JP2017025305A - Colorant and method for producing the same, coloring composition, colored cured film and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition that has excellent brightness and heat resistance and can inhibit its migration property.SOLUTION: The present invention provides a coloring composition comprising (A) a colorant, (B) a binder resin, and (C) a polymerizable compound, where a compound represented by formula (1) is included, as (A) colorant [Rto Rand Rare a univalent group, respectively; Rand Rare H or a univalent group; Zeach independently represents a-valent onium cation; where, two or more of Rto Rare a univalent group having -CO, -SO, or the like; a is an integer of 1 or more; x is an integer of 0 to 5; y and z each is an integer of 0 to 3].SELECTED DRAWING: None

Description

  The present invention relates to a colorant and a method for producing the same, a colored composition, a colored cured film, and a display element. More specifically, the present invention relates to a transmissive or reflective color liquid crystal display element, solid-state imaging element, organic EL display element, and electronic paper. Coloring agents suitably used for the production of colored cured films used in the field and the like, methods for producing the same, colored compositions containing the colorants, colored cured films containing the colorants, and displays comprising the colored cured films It relates to an element.

  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.

  However, a color filter using a pigment as a colorant tends to cause a decrease in luminance and contrast of the display element due to light scattering by pigment particles. On the other hand, in a color filter using a dye as a colorant, heat resistance and solubility in an organic solvent are easily deteriorated as compared with the case of using a pigment, and the other color pixel adjacent to the dye in the pixel of the color pattern In addition, the brightness of the display element may be lowered by color transfer to a cured film that does not contain a colorant such as a protective film (hereinafter also referred to as “transferability”).

  Therefore, in order to improve heat resistance, solvent resistance, and the like, a coloring composition containing a salt-forming compound of an anionic dye and a cation as a colorant (Patent Document 1), an anionic dye and a cationic resin A coloring composition containing a salt-forming compound is proposed (Patent Document 2).

Japanese Patent No. 4492760 Japanese Patent No. 4873101

  The subject of this invention is providing the coloring composition which can form the colored cured film which was excellent in the brightness | luminance and heat resistance, and the dye transfer property was suppressed. Furthermore, the subject of this invention is providing the coloring agent used for the said coloring composition, its manufacturing method, the colored cured film containing this coloring agent, and the display element which comprises this colored cured film.

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

That is, the present invention is a colored composition containing (A) a colorant, (B) a binder resin, and (C) a polymerizable compound,
(A) A colored composition containing a compound represented by the following formula (1) as a colorant is provided.

  The present invention also provides a compound represented by the following formula (1), a colored cured film containing the compound, and a display element comprising the colored cured film. Here, the “colored cured film” means each color pixel, black matrix, black spacer, and the like used for a display element and a solid-state imaging element.

[In Formula (1),
R ^{1 to} R ⁴ and R ⁷ each independently represent a monovalent group.
R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent group, provided that at least one of R ⁵ and R ⁶ represents a monovalent group.
Z ^{a +} represents an a-valent onium cation.
a represents an integer of 1 or more.
b represents an integer of 1 or more determined so that the compound represented by the formula (1) is electrically neutral. When b is 2 or more, a plurality of (Z ^{a +} ) may be the same or different. Also good.
x shows the integer of 0-5.
y and z each independently represent an integer of 0 to 3.
However, two or more of R ^{1 to} R ⁷ are —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^— , or one having —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^—. Is a valent group. ]

  The present invention further includes a step of reacting a compound having the structure represented by formula (100) with a compound represented by formula (101) in the presence of a base, and a structure represented by formula (102) The manufacturing method of the compound which has this is provided.

[In Formula (100),
R ^{1 to} R ⁴ and R ⁷ each independently represent a monovalent group.
x shows the integer of 0-5.
y and z each independently represent an integer of 0 to 3.
Provided that at least two of R ^{1 to} R ⁴ and R ⁷ are —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^— , or —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^—. It is a monovalent group having ]

[In Formula (101),
R represents a monovalent hydrocarbon group.
X represents Br, I or OT _f .
_Tf represents a trifluoromethylsulfonyl group. ]

[In Formula (102),
R ^{1 to} R ⁴ and R ⁷ each independently represent a monovalent group.
R independently represents a monovalent hydrocarbon group.
x shows the integer of 0-5.
y and z each independently represent an integer of 0 to 3.
Provided that at least two of R ^{1 to} R ⁴ and R ⁷ are —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^— , or —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^—. It is group which has. ]

  If the coloring composition of this invention is used, the colored cured film which was excellent in the brightness | luminance and heat resistance, and the dye transfer property was suppressed 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 this invention contains the compound (henceforth "this coloring agent") represented by following formula (1) as a coloring agent.

[In Formula (1),
R ^{1 to} R ⁴ and R ⁷ each independently represent a monovalent group.
R ⁵ and R ⁶ independently of each other represent a hydrogen atom or a monovalent group, provided that at least one of R ⁵ and R ⁶ represents a monovalent group;
Z ^{a +} represents an a-valent onium cation.
a represents an integer of 1 or more.
b represents an integer of 1 or more determined so that the compound represented by the formula (1) is electrically neutral. When b is 2 or more, a plurality of (Z ^{a +} ) may be the same or different. Also good.
x shows the integer of 0-5.
y and z each independently represent an integer of 0 to 3.
However, two or more of R ^{1 to} R ⁷ are —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^— , or one having —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^—. Is a valent group. ]

In the formula (1), examples of the monovalent group according to R ^{1 to} R ⁷ include a monovalent group containing a hetero atom and a monovalent hydrocarbon group.
Examples of the monovalent group containing a hetero atom include a halogen atom, —CO ₂ ⁻ , —SO ₃ ^— , —PO ₄ ^— , —OR ⁸ , —SR ⁸ , —NR ⁸ R ⁹ , —CO ₂ M, _{^{-CO 2 R 8, -SO 3 M}} , -SO 3 R 8, -SO 2 NR 8 R 9, -SO 2 -O-N = CR 8 R 9, -SO 2 NHNHR 8, -SO 2 SR 8, and the like can be given -SO ₂ NHSO ₂ R ^8. Here, R ⁸ and R ⁹ each independently represent a hydrogen atom or a monovalent hydrocarbon group, and M represents a sodium atom or a potassium atom.

The monovalent hydrocarbon group may be any of a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. Further, the monovalent aliphatic hydrocarbon group may be either linear or branched, and the monovalent aliphatic hydrocarbon group and the monovalent alicyclic hydrocarbon group are saturated carbon atoms. It may be a hydrogen group or an unsaturated hydrocarbon group. The position of the unsaturated bond of the unsaturated hydrocarbon group may be either in the molecular chain or at the end of the molecular chain, and can be at any position. Here, in the present specification, the “alicyclic hydrocarbon group” is a concept excluding an aliphatic hydrocarbon group having no cyclic structure. In addition, in this specification, “alicyclic hydrocarbon group” and “aromatic hydrocarbon group” are not only a group consisting of only a ring structure, but also a divalent aliphatic hydrocarbon group substituted on the ring structure. In other words, the structure includes at least an alicyclic hydrocarbon or an aromatic hydrocarbon. Further, the monovalent hydrocarbon group may have a substituent within a range not departing from the gist of the present invention. The position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different. Examples of the substituent include a cyano group, a formyl group, a nitro group, a trialkylsilyl group, a heterocyclic group, etc., in addition to the above-described monovalent group and monovalent aliphatic hydrocarbon group containing a hetero atom. . Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkoxyl group according to —OR ⁸ may be either linear or branched, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a tert-butoxy group. Examples of the aryloxy group include a phenoxy group and a benzyloxy group. Among them, the substituent preferably has at least one selected from a monovalent group containing a hetero atom and a monovalent aliphatic hydrocarbon group. Incidentally, it is possible to employ the same configuration as the monovalent hydrocarbon radicals be monovalent hydrocarbon radical according to R ⁸ and R ⁹ according to R ¹ to R ^7.

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

Examples of the monovalent alicyclic hydrocarbon group include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged ring hydrocarbon group, a spiro hydrocarbon group, and a cyclic terpene hydrocarbon group. Can do. Carbon number of an aliphatic hydrocarbon group becomes like this. Preferably it is 3-30, More preferably, it is 3-20, More preferably, it is 3-12. Specific examples of the cycloalkyl group include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a t-butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. Specific examples of the cycloalkenyl group include Examples thereof include 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 monovalent aromatic hydrocarbon group include an aryl group and an aralkyl group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenylene group, an azulenyl group, and a 9-fluorenyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, A trityl group etc. are mentioned.

In the present invention, two or more of R ^{1 to} R ⁷ are —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^— , or —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^—. In which at least two of R ^{1 to} R ⁷ are —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^— , or —CO ₂ ^— , — A hydrocarbon group having SO ₃ ^— or —PO ₄ ^— is preferable, and two or more of R ^{1 to} R ⁷ are —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^— , or as a substituent. An aromatic hydrocarbon group having —CO ₂ ^— or —SO ₃ ^— is more preferable. In addition, when it is a monovalent group having —CO ₂ ^— , —SO ₃ ^—, or —PO ₄ ^— , the monovalent group is other than —CO ₂ ^— , —SO ₃ ^—, or —PO ₄ ^—. It may further have a substituent.

In the formula (1), preferred embodiments are as follows.
R ¹ is preferably —CO ₂ ^— or —SO ₃ ^— , and x is preferably 1.
y and z are preferably 0.
R ⁴ is preferably a substituted or unsubstituted aromatic hydrocarbon group, and more preferably a substituted or unsubstituted phenyl group.
R ⁵ and R ⁶ are preferably each independently a substituted or unsubstituted aliphatic hydrocarbon group, and more preferably a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms.
R ⁷ is preferably an aromatic hydrocarbon group having —SO ₃ ^— as a substituent, and more preferably a phenyl group having —SO ₃ ^— as a substituent.

Examples of the onium cation according to Za ⁺ include an ammonium cation, a phosphonium cation, a sulfonium cation, an iodonium cation, a diazonium cation, a resin having an ammonium base, a resin having a phosphonium base, a resin having a sulfonium base, a resin having an iodonium base, Mention may be made of resins having a diazonium base. Among these, an ammonium cation, a phosphonium cation, a resin having an ammonium base, and a resin having a phosphonium base are preferable.

As the ammonium cation, an ammonium cation having 1 to 4 substituted or unsubstituted hydrocarbon groups is preferable, and an ammonium cation having 3 to 4 substituted or unsubstituted hydrocarbon groups is more preferable. Specific examples thereof include, for example, tetramethylammonium, tetraethylammonium, tetrabutylammonium, monostearyltrimethylammonium, distearyldimethylammonium, tristearylmonomethylammonium, cetyltrimethylammonium, trioctylmethylammonium, dioctyldimethylammonium, monolauryl. Tetraalkylammonium such as trimethylammonium, dilauryldimethylammonium, trilaurylmethylammonium; aryl such as triamylbenzylammonium, trihexylbenzylammonium, trioctylbenzylammonium, trilaurylbenzylammonium, benzyldimethylstearylammonium, benzyldimethyloctylammonium Mention may be made of dodecyl ammonium, 2-monoalkyl ammonium ethylhexyl and ammonium and the like; trialkyl ammonium; dialkylammonium such as di-butyl ammonium; trialkylammonium decyl dimethyl ammonium. The ammonium cation may have a polymerizable unsaturated group. Examples of such an ammonium cation include (meth) acryloyloxyethyltrimethylammonium, (meth) acryloyloxyethyltriethylammonium, and (meth) acryloyloxyethyl. Ammonium having a (meth) acryloyloxy group such as diethylhexylammonium, (meth) acryloyloxyethyldimethylbenzylammonium, (meth) acryloyloxyethylmethylmorpholinoammonium; (meth) acryloylaminopropyltrimethylammonium, (meth) acryloylaminoethyl (Meth) acryloylamino groups such as triethylammonium and (meth) acryloylaminoethyldimethylbenzylammonium Ammonium; dimethyldiallylammonium, and tri-methyl vinyl phenyl ammonium, and the like. Among these, tetraalkylammonium and ammonium having a polymerizable unsaturated group are preferable, and tetra (C _1-18 alkyl) ammonium and ammonium having a (meth) acryloyloxy group are more preferable. The molecular weight of the ammonium cation is preferably less than 1,000 and more preferably 700 or less. The molecular weight of the ammonium cation is preferably 100 or more, more preferably 200 or more.

The phosphonium cation is preferably a phosphonium cation having 1 to 4 substituted or unsubstituted hydrocarbon groups, and more preferably a phosphonium cation having 3 to 4 substituted or unsubstituted hydrocarbon groups. Specific examples thereof include, for example, tetraalkylphosphonium such as tetrabutylphosphonium, methyltrioctylphosphonium, octyltributylphosphonium, dodecyltributylphosphonium, hexadecyltributylphosphonium, dihexyldioctylphosphonium, aryltrialkylphosphonium such as benzyltributylphosphonium, Examples thereof include dialkyldiarylphosphonium such as dibutyldiphenylphosphonium, alkyltriarylphosphonium such as butyltriphenylphosphonium, and tetraarylphosphonium such as benzyltriphenylphosphonium. Among these, tetraalkylphosphonium is preferable, and tetra (C _1-18 alkyl) phosphonium is more preferable. The molecular weight of the phosphonium cation is preferably less than 1,000, and more preferably 700 or less. The molecular weight of the phosphonium cation is preferably 100 or more, more preferably 200 or more.

  As a resin having an ammonium base or a resin having a phosphonium base, for example, a vinyl resin having a structural unit represented by the following formula (2) is preferable.

[In Formula (2),
R ^{10 to} R ¹³ each independently represent a hydrogen atom or a monovalent hydrocarbon group, and two of R ^{11 to} R ¹³ may be bonded to each other to form a ring.
L represents a divalent organic group,
Q represents a nitrogen atom or a phosphorus atom. ]

The monovalent hydrocarbon group according to R ^{10 to} R ¹³ may be any of a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. The configuration is as described in R ^{1 to} R ⁷ .
Examples of the divalent organic group related to L include a group formed by combining a divalent hydrocarbon group, a divalent hydrocarbon group, and a linking group containing atoms other than carbon atoms and hydrogen atoms. Examples of such an organic group include an alkanediyl group, an arylene group, an arylenealkanediyl group, —CONH—R ¹⁴ —, —COO—R ¹⁴ —, and the like. Here, R ¹⁴ represents an alkanediyl group.

The alkanediyl group may be linear or branched. For example, a methylene group, ethylene group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane- 1,3-diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4-diyl Group, pentane-1,5-diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, etc. Mention may be made of 1 to 10 alkanediyl groups. Incidentally, it is possible to employ the same configuration as the alkanediyl group which may alkanediyl group according to R ¹⁴ according to the L.
Examples of the arylene group include arylene groups having 6 to 10 carbon atoms such as a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group. 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. For example, a phenylenemethylene group, a phenylenedimethylene group, a phenylenetrimethylene group, a phenylenetetramethylene group, or a phenylenepentamethylene group. And a phenylene C _1-6 alkanediyl group such as a phenylenehexamethylene group.

Among them, as R ^10, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group.
As R < ¹¹ > -R < ¹³ >, an alkyl group and an aryl group are preferable, and a C1-C12 alkyl group and a C6-C10 aryl group are still more preferable. R ^{11 to} R ¹³ may be the same or different.
L is preferably —CONH—R ¹⁴ — or —COO—R ¹⁴ —, and R ¹⁴ is preferably an alkanediyl group having 1 to 4 carbon atoms.
Q can be appropriately selected from a nitrogen atom and a phosphorus atom.

  The vinyl resin having the structural unit represented by the formula (2) can be produced by an appropriate method. For example, a monomer containing an ethylenically unsaturated monomer having an ammonium base is polymerized. A method of polymerizing a monomer containing an ethylenically unsaturated monomer having an amino group to obtain a vinyl resin having an amino group, and then reacting with an onium chlorinating agent to ammonium chloride, or a phosphonium base Examples thereof include a method of polymerizing a monomer containing an ethylenically unsaturated monomer.

  Examples of the ethylenically unsaturated monomer having an ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) Alkyl (meth) acrylate-based quaternary ammonium salts such as acryloyloxyethyldimethylmorpholino ammonium chloride; (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzylammonium Alkyl (meth) acryloylamide quaternary ammonium salts such as chloride; Luzia Lil ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

  Examples of the ethylenically unsaturated monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, and dibutylamino. Ethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl Aminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butyl (Meth) acrylic acid ester or (meth) acrylamide having a dialkylamino group such as minopropyl (meth) acrylamide; styrene having a dialkylamino group such as dimethylaminostyrene or dimethylaminomethylstyrene; diallylamine compounds such as diallylmethylamine or diallylamine Amino group-containing aromatic vinyl monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone, and N-vinylcarbazole.

  Examples of the onium chloride agent include alkyl sulfates such as dimethyl sulfate, diethyl sulfate and dipropyl sulfate; sulfonate esters such as methyl p-toluenesulfonate and methyl benzenesulfonate; methyl chloride, ethyl chloride, propyl chloride, octyl chloride and the like. Alkyl bromides such as methyl bromide, ethyl bromide, propyl bromide, octyl chloro bromide; benzyl chloride or benzyl bromide.

  In the reaction between the vinyl resin having an amino group and the onium chlorinating agent, an equimolar amount or less of onium chlorinating agent is usually added dropwise to the vinyl resin solution having an amino group. The reaction temperature is usually about 90 ° C. or lower, and the reaction time is usually about 1 to 4 hours.

  Examples of the ethylenically unsaturated monomer having a phosphonium base include (meth) acryloyloxymethyltributylphosphonium chloride, (meth) acryloyloxyethyltriethylphosphonium chloride, (meth) acryloyloxyethyltributylphosphonium chloride, (meth) acryloyl. Alkyl such as oxyethyltributylphosphonium bromide, (meth) acryloyloxyethyltributylphosphonium iodide, (meth) acryloyloxypropyltributylphosphonium chloride, (meth) acryloyloxybutyltributylphosphonium chloride, (meth) acryloyloxyethyltrioctylphosphonium chloride (Meth) acrylate phosphonium salts are mentioned. These compounds can also be synthesized with reference to, for example, JP-A-9-255694.

  The vinyl resin may have a structural unit other than the structural unit represented by the formula (2). Examples of the ethylenically unsaturated monomer that gives a structural unit other than the structural unit represented by the formula (2) include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, Examples thereof include fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol, aromatic vinyl compounds, (meth) acrylonitrile, N-substituted maleimides, monomers having an acid group, and the like. . Examples of the monomer having an acid group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid , Unsaturated dicarboxylic acids such as itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like; trivalent or higher unsaturated polycarboxylic acids or anhydrides thereof; succinic acid mono (2-acryloyl) Roxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), etc. Mono [(meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprola Like tons mono (meth) acrylates of both-terminal carboxy polymers such monomethacrylate and the like. Examples of the aromatic vinyl compound and the N-substituted maleimide include those described later as examples of unsaturated monomers constituting the binder resin.

A known method can be employed for the polymerization reaction, and examples thereof include anionic polymerization, living anion polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization.
The content ratio of the structural unit represented by the formula (2) in the vinyl resin is preferably 4 to 74% by mass, and more preferably 8 to 48% by mass in all the structural units.
The molecular weight of the vinyl resin is preferably 1,000 to 500,000, more preferably 3,000 to 15,000, as a weight average molecular weight measured by gel permeation chromatography (GPC).
The amount of the ammonium base present in the vinyl resin is not particularly limited, but the ammonium salt value is preferably 10 to 200 mgKOH / g, more preferably 20 to 130 mgKOH / g.

  The colorant can be produced, for example, by a salt exchange reaction between an anionic xanthene chromophore salt-forming compound having a structure represented by the formula (1) and an onium cation. In addition, the salt-forming compound referred to in this paragraph means a salt of an anionic xanthene chromophore and a proton or a valent metal cation, and a has the same meaning as a in formula (1). Examples of such a-valent metal cations include monovalent metal cations such as sodium ion, potassium ion, cesium ion, and silver ion, magnesium ion, calcium ion, barium ion, copper (II) ion, and iron (II) ion. And divalent metal cations such as zinc (II) ion and lead (II) ion, and trivalent metal cations such as aluminum ion and iron (III) ion.

  Further, for example, when the present colorant has a structure represented by the following formula (102), a compound having a structure represented by the following formula (100) in the presence of a base, and the following formula (101) It can also manufacture by using for the process including the process (henceforth "process (1)") with which the compound represented by these is made to react. The compound having the structure represented by the following formula (100) and the compound having the structure represented by the following formula (102) are exemplified as the counter cation in paragraph [0047] in addition to the above onium cation. It may have a metal cation or proton such as sodium ion, potassium ion, calcium ion or barium ion.

[In Formula (102),
R ^{1 to} R ⁴ and R ⁷ each independently represent a monovalent group,
R represents a monovalent hydrocarbon group;
x shows the integer of 0-5.
y and z each independently represent an integer of 0 to 3.
Provided that at least two of R ^{1 to} R ⁴ and R ⁷ are —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^— , or —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^—. It is a monovalent group having ]

[In Formula (100), R < ¹ > -R < ⁴ > and R < ⁷ >, x, y, and z are synonymous with the above. ]

[In Formula (101),
R is as defined above,
X represents Br, I or OT _f ;
_Tf represents a trifluoromethylsulfonyl group. ]

In the formula (101) and the formula (102), the monovalent hydrocarbon group according to R is a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, or a monovalent aromatic hydrocarbon group. either good, its specific configuration is as described in R ¹ to R ^7. Moreover, the monovalent hydrocarbon group according to R may have a substituent, the position and number of the substituent are arbitrary, and when having two or more substituents, the substituents are the same or different. May be. Specific examples of the substituent include the same ones as exemplified in the monovalent hydrocarbon group according to R ^{1 to} R ⁷ . Among them, R is preferably a substituted or unsubstituted aliphatic hydrocarbon group, and more preferably a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Two Rs may be the same or different, but are preferably the same.
In Formula (101) and Formula (102), the specific configurations of R ^{1 to} R ⁴ and R ⁷ , x, y, and z are as described in Formula (1).

  Examples of the compound having a structure represented by the formula (102) include C.I. I. Acid Red 289, C.I. I. Acid violet 9 is mentioned.

As the base, a base containing a metal element is preferable, and examples thereof include metal carbonates, metal hydrogen carbonates, metal hydroxides, metal alkoxides, and metal hydrides.
Examples of the metal carbonate include alkali metal carbonate and alkaline earth metal carbonate. Examples of the alkali metal carbonate include potassium carbonate, sodium carbonate, lithium carbonate, and cesium carbonate. Examples of the alkaline earth metal carbonate include magnesium carbonate and calcium carbonate.
The metal hydrogen carbonate is preferably an alkali metal hydrogen carbonate, and examples thereof include sodium hydrogen carbonate and potassium hydrogen carbonate.
Examples of the metal hydroxide include alkali metal hydroxides and alkaline earth metal hydroxides. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide. Among these, sodium hydroxide and potassium hydroxide are preferable. Examples of the alkaline earth metal hydroxide include magnesium hydroxide and calcium hydroxide.
Examples of the metal alkoxide include alkali metal alkoxides and alkaline earth metal alkoxides. Examples of the alkali metal alkoxide include sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium tert-butoxide, lithium methoxide, lithium isopropoxide. Lithium tert-butoxide. Examples of the alkaline earth metal alkoxide include magnesium methoxide and magnesium ethoxide.
Examples of the metal hydride include sodium hydride and calcium hydride.

  Among these bases, metal carbonates and metal hydroxides are preferable, alkali metal carbonates, alkali metal hydroxides, and alkaline earth metal hydroxides are more preferable, and alkali metal hydroxides are still more preferable. According to such an embodiment, the present colorant or its precursor can be synthesized in a high yield, the time required for the synthesis of this colorant or its precursor can be shortened, and further, the by-product of the byproduct can be reduced. You can reduce life.

  Such a reaction is usually carried out in the presence of a solvent. Examples of the solvent include water; halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; ketones such as methyl isobutyl ketone; amides such as dimethylformamide, N, N-dimethylacetamide and 1-methyl-2-pyrrolidone; ethyl lactate and the like (Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, cyclohexanol; (poly) alkylenes such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether Glycol monoalkyl ethers; keto alcohols such as diacetone alcohol; fatty acid alkyls such as ethyl acetate, n-butyl acetate, n-amyl formate, i-amyl acetate, ethyl butyrate, etc. Kill ester; etc. are mentioned. Of these, water, ketone, amide, alkyl lactate ester, (cyclo) alkyl alcohol, (poly) alkylene glycol monoalkyl ether, and fatty acid alkyl ester are preferable.

  The reaction temperature is preferably 30 to 180 ° C, more preferably 70 to 150 ° C. The reaction time is preferably 1 to 8 hours, more preferably 3 to 6 hours.

  The amount of the compound represented by formula (101) to be used is preferably 2 to 10 mol, more preferably 2 to 5 mol, per 1 mol of the compound represented by formula (100).

  After the reaction, a step of isolating the compound represented by the formula (102) from the reaction mixture may be included. The isolation method is not particularly limited, and a purification method commonly used in organic synthetic chemistry, for example, filtration, extraction, washing, drying, concentration, recrystallization, various chromatographies and the like can be combined as necessary.

  The coloring composition of the present invention can also be used by mixing other colorants other than the present colorant. 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 present colorant, and other colorants can be used alone or in combination of two or more. Among them, an organic pigment is preferable as the pigment and an organic dye is preferable as the dye from the viewpoint of obtaining a pixel having high luminance, contrast, and coloring power.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), that is, the following color index (CI) numbers. Can be mentioned.

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. Pigment red 264, C.I. I. Red pigments such as CI Pigment Red 269;
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. 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. Purple pigment such as CI Pigment Violet 23.
In addition, JP-A-2001-081348, JP-A-2010-026334, JP-A-2010-237384, JP-A-2010-237369, JP-A-2011-006602, JP-A-2011-145346, etc. Can be mentioned.

  Especially, the coloring composition of this invention can be preferably used for formation of a blue pixel and a red pixel, and can be preferably used especially for formation of a blue pixel. When used for forming a blue pixel, it preferably contains at least one selected from the group consisting of blue pigments and purple pigments. I. Pigment blue 15: 6 and C.I. I. More preferably, at least one selected from the group consisting of CI Pigment Violet 23 is included. On the other hand, when the colored composition of the present invention is used for forming a red pixel, it preferably contains at least one selected from the group consisting of a red pigment and a yellow pigment. I. Pigment red 177, C.I. I. Pigment red 254, C.I. I. Pigment red 264, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. More preferably, at least one selected from the group consisting of CI Pigment Yellow 185 is included. Thereby, a colored cured film, particularly a blue pixel, which is excellent in luminance and heat resistance and has suppressed dye transfer property can be easily formed.

  Moreover, as a dye, a triarylmethane dye, an anthraquinone dye, a dipyrromethene dye, or the like is preferable. More specifically, WO2010 / 123071 pamphlet, JP2011-116803A, JP2011-117995A, JP2011-133844A, JP2011-174987A, and JP2010. No. 085454, compounds described in paragraphs [0017] to [0105], JP2011-164594A, paragraphs [0014] to [0095], JP2012-140586, paragraph [0025] ] The organic dye as described in the compound etc. as described in [0058] can be mentioned.

  In the present invention, other pigments to be arbitrarily mixed 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.

  Moreover, in this invention, a well-known dispersing agent and a dispersing aid can also be contained with 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, Ajisper PB881 (or, Ajinomoto Fine-Techno Co., Ltd.) other such, BYK-LPN21324 the (Chemie (BYK) Co., Ltd.) can be mentioned, respectively.

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

  The content of other colorants is preferably 95% by mass or less, more preferably 90% by mass or less, based on the total content of the colorants. The lower limit is not particularly limited and may be 0.01% by mass or more.

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

-(B) Binder resin-
(B) Although binder resin is not specifically limited, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and 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)”). . (B) 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 a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran), usually from 1,000 to 100,000. Preferably it is 3,000-50,000. By setting it as such an aspect, while heat resistance and solvent resistance are improved further, dye transfer property and foreign material generation can be suppressed effectively.

  Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3. .0. In addition, Mn here says the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).

  (B) The binder resin can be produced by a known method, and is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 2007/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

  In this invention, content of (B) 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. By setting it as such an aspect, not only the storage stability of a coloring composition improves and the brightness | luminance and heat resistance of a cured film are improved, but transferability and generation | occurrence | production of a foreign material can be suppressed effectively. .

-(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 polyfunctional (meth) acrylate, which is a reaction product of an aliphatic polyhydroxy compound and (meth) acrylic acid, and a polyfunctional (meta) modified with caprolactone. ) Acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate which is a reaction product of (meth) acrylate having hydroxyl group and polyfunctional isocyanate, (meth) acrylate having hydroxyl group and acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group which is a reaction material with a thing can be mentioned.

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

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

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

  Among these polymerizable compounds, polyfunctional (meth) acrylate, which is a reaction product 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 polyfunctional (meth) acrylates, which are a reaction product of a trivalent or higher aliphatic polyhydroxy compound 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 compound of pentaerythritol triacrylate and succinic anhydride, a reaction compound of dipentaerythritol pentaacrylate and succinic anhydride, It is particularly preferable because it has high strength, excellent 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 setting it as such an aspect, the pixel which was excellent in the brightness | luminance and heat resistance, the dye transfer property was suppressed, or the black matrix and the black spacer excellent in light-shielding property can be formed.

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

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

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

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

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

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

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

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like. As commercial products of O-acyloxime compounds, 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 setting it as such an aspect, not only suppression of the generation | occurrence | production of a foreign material but sclerosis | hardenability and a film characteristic can be made favorable.

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

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

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

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

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

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

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

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

  The colored composition of the present invention can be prepared by an appropriate method. For example, the components (A) to (C) are mixed together with a solvent and other components optionally added. Can be prepared. (A) When a pigment is used together with the present colorant as a colorant, the pigment is pulverized in a solvent in the presence of a dispersant and optionally (B) a part of the binder resin, for example, using a bead mill, a roll mill or the like. While mixing and dispersing to make a pigment dispersion, the colorant and (C) polymerizable compound, and (B) a binder resin, a photopolymerization initiator, and further added to this pigment, if necessary. A method of preparing by adding a solvent and other components and mixing them is preferred.

Colored cured film and method for forming the same The colored cured film of the present invention contains the compound represented by the above formula (1) and can be formed using the colored composition of the present invention. Specific examples of the colored cured film include each color pixel, black matrix, spacer, insulating film and the like used in display elements and solid-state imaging elements.

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 example 1
To a 200 mL eggplant-shaped flask containing a stirrer, 20 g of Acid Red 289, 18.4 g of ethyl iodide, 3.32 g of potassium hydroxide and 120 g of ultrapure water were added and stirred for 6 hours under reflux. After cooling to room temperature, the aqueous layer was washed with 80 g of hexane, and this operation was repeated three times. Thereafter, 150 g of 2N hydrochloric acid was added to precipitate the reaction product, and the supernatant was removed. Subsequently, 100 g of ultrapure water was added, 50 g of 2N hydrochloric acid was added again to precipitate the reaction product, and the supernatant was removed. The obtained precipitate was dried under reduced pressure to obtain 11.9 g of a solid. Analysis by LC-MS and ¹ H-NMR confirmed that the obtained solid was a mixture of dyes composed mainly of compounds represented by the following formulas (A1-1) and (A1-2). It was. This compound is defined as a colorant (A-1).

Synthesis example 2
In Synthesis Example 1, the same reaction operation as in Synthesis Example 1 was performed except that 10.9 g of 1-iodobutane was used instead of 18.4 g of ethyl iodide. Analysis by LC-MS and ¹ H-NMR confirmed that the obtained solid was a mixture of pigments composed mainly of compounds represented by the following formulas (A2-1) and (A2-2). It was. Let this compound be a coloring agent (A-2).

Synthesis example 3
In Synthesis Example 1, the same reaction operation as in Synthesis Example 1 was performed except that 18.4 g of 1-iodooctane was used instead of 18.4 g of ethyl iodide. Analysis by LC-MS and ¹ H-NMR confirmed that the obtained solid was a mixture of dyes composed mainly of compounds represented by the following formulas (A3-1) and (A3-2). It was. This compound is defined as a colorant (A-3).

(Synthesis of this colorant)
Example 1
3 g of the colorant (A-1) obtained in Synthesis Example 1, 1.3 g of tetrabutylammonium bromide, 18 g of ultrapure water, and 9 g of acetonitrile were added to a 100 mL eggplant flask containing a stir bar and stirred at room temperature for 2 hours. . Thereafter, 9 g of ethyl acetate was added, liquid separation was performed, and the aqueous layer was separated. Then, 20 g of ion-exchanged water was added, and the aqueous layer was separated again. Thereafter, the organic layer was washed twice with 20 g of ion-exchanged water and 4 g of acetonitrile. Subsequently, the organic layer was concentrated under reduced pressure using a rotary evaporator. The obtained oily residue was dried under reduced pressure at 50 ° C. for 12 hours to obtain 1.4 g of a solid. Analysis by LC-MS and ¹ H-NMR confirmed that the obtained solid was a mixture of dyes composed mainly of compounds represented by the following formulas (A4-1) and (A4-2). It was. This compound is defined as a colorant (A-4).

Example 2
In Example 1, the same reaction operation as in Example 1 was performed except that 1.4 g of tetrabutylphosphonium bromide was used instead of 1.3 g of tetrabutylammonium bromide. Analysis by LC-MS and ¹ H-NMR confirmed that the obtained solid was a mixture of dyes composed mainly of compounds represented by the following formulas (A5-1) and (A5-2). It was. This compound is defined as a colorant (A-5).

Example 3
In Example 2, the same reaction as in Example 2 except that 3 g of the colorant (A-2) obtained in Synthesis Example 2 was used instead of 3 g of the colorant (A-1) obtained in Synthesis Example 1. The operation was performed. Analysis by LC-MS and ¹ H-NMR confirmed that the obtained solid was a mixture of dyes composed mainly of compounds represented by the following formulas (A6-1) and (A6-2). It was. This compound is defined as a colorant (A-6).

Example 4
In Example 2, the same reaction as in Example 2 except that 3 g of the colorant (A-3) obtained in Synthesis Example 3 was used instead of 3 g of the colorant (A-1) obtained in Synthesis Example 1. The operation was performed. Analysis by LC-MS and ¹ H-NMR confirmed that the obtained solid was a mixture of pigments composed mainly of compounds represented by the following formulas (A7-1) and (A7-2). It was. This compound is defined as a colorant (A-7).

Example 5
In Example 1, the same reaction operation as in Example 1 was carried out except that 2.3 g of dimethyldioctadecyl ammonium chloride was used instead of 1.3 g of tetrabutylammonium bromide. Analysis by LC-MS and ¹ H-NMR confirmed that the obtained solid was a mixture of dyes composed mainly of compounds represented by the following formulas (A8-1) and (A8-2). It was. This compound is defined as a colorant (A-8).

Example 6
In Example 1, the same reaction operation as in Example 1 was performed except that 1.4 g of 2-acryloyloxyethyl diethylhexylammonium bromide was used instead of 1.3 g of tetrabutylammonium bromide. Analysis by LC-MS and ¹ H-NMR confirmed that the obtained solid was a mixture of dyes composed mainly of compounds represented by the following formulas (A9-1) and (A9-2). . This compound is defined as a colorant (A-9).

Example 7
3 g of the colorant (A-1) obtained in Synthesis Example 1 and a method described in paragraph [0156] of Japanese Patent No. 4873101, in a 100 mL eggplant flask containing a stir bar, an ammonium base in the side chain 13 g of a 47% strength by weight solution containing a resin having 20 wt% and 20 g of methanol were added and stirred for 30 minutes. Thereafter, the reaction solution was concentrated under reduced pressure using a rotary evaporator. 9 g of acetonitrile and 9 g of ethyl acetate were added to the obtained residue, and the contents were stirred at 50 ° C. for 30 minutes. Next, 18 g of ion-exchanged water was added for liquid separation, and the aqueous layer was separated. Then, 20 g of ion-exchanged water was added, and the aqueous layer was separated again. Thereafter, the organic layer was washed once with 20 g of ion-exchanged water and 4 g of acetonitrile. Subsequently, the organic layer was concentrated under reduced pressure using a rotary evaporator. The obtained residue was dried under reduced pressure at 50 ° C. for 12 hours to obtain 4.3 g of a solid. As a result of analysis by LC-MS and ¹ H-NMR, the obtained solid was obtained from an anionic xanthene chromophore represented by the following formulas (A10-1) and (A10-2), and methacryloyloxyethyltrimethylammonium chloride. It was confirmed to be a mixture of pigments mainly composed of a salt with a resin anion having a repeating unit derived therefrom. This compound is defined as a colorant (A-10). The resin having an ammonium base in the side chain was obtained by reacting a copolymer of methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and dimethylaminoethyl methacrylate with methyl chloride as an onium chloride agent. The weight average molecular weight is 6,830, and the ammonium salt value is 34 mgKOH / g.

Comparative Example 1
According to the method described in paragraph [0128] of Japanese Patent No. 4492760, a compound represented by the following structural formula was synthesized. Let the obtained compound be a coloring agent (a1).

Comparative Example 2
According to the method described in paragraph [0162] of JP2013-50693A, a compound represented by the following structural formula was synthesized. Let the obtained compound be a coloring agent (a2).

Comparative Example 3
According to the method described in paragraph [0201] of JP2013-235257A, a compound represented by the following structural formula was synthesized. Let the obtained compound be a coloring agent (a3).

  Next, the reaction rates in the alkylation reaction were compared based on the following method.

(Alkylation reaction using alkali metal carbonate)
Example 8
20 g of Acid Red 289, 10.9 g of butyl iodide, 8.2 g of potassium carbonate and 120 g of ultrapure water were added to a 200 mL eggplant-shaped flask containing a stir bar. The temperature of the oil bath was set to 110 ° C., and heating and stirring were started. The reaction solution was sampled 1 hour and 4 hours after the start of heating and stirring, and the reaction rate was measured under the HPLC conditions described below.

(Alkylation using alkali metal hydroxide)
Example 9
In Example 8, an alkylation reaction was carried out by the same reaction operation as in Example 8 except that 3.3 g of potassium hydroxide was used instead of 8.2 g of potassium carbonate, and measurement was performed.

  The chemical identification of each compound represented by the formulas (α0), (α1A), (α1B), (α2) and (β0) to (β2) contained in the solutions sampled in Examples 8 and 9 was determined by LC-MS. It went by.

[LC-MS measurement conditions]
・ Equipment; LCQ Freeet [Ultimate 3000, manufactured by Thermo Scientific Co., Ltd.]
・ Ionization; ESI Negative
Scan range: 100-1500

Formula (α0): Measured value ([M−H] ⁻ ); 653.1,
Calculated value (Exact Mass); 653.1

Formula (α1A), Formula (α1B): Measured value ([M−H] ⁻ ); 709.2,
Calculated value (Exact Mass); 709.2

Formula (α2): measured value ([M−H] ⁻ ); 765.3,
Calculated value (Exact Mass); 765.3

Formula (β0): Measured value ([M−H] ⁻ ); 733.1,
Calculated value (Exact Mass); 733.1

Formula (β1): Measured value ([M−H] ⁻ ); 789.2
Calculated value (Exact Mass); 789.2

Formula (β2): Measured value ([M−H] ⁻ ); 845.2,
Calculated value (Exact Mass); 845.2

[HPLC analysis conditions]
Apparatus: High-performance liquid chromatograph [Ultimate 3000, manufactured by Thermo Scientific Co., Ltd.]
・ Column: CAPCELLPAK C18 MG (5μ150x4.6mm, manufactured by Shiseido) and CAPCELLPAK C18 MG (5μ35x4.6mm, manufactured by Shiseido) connected

・ Detection wavelength: 254 nm
-Column oven set temperature: 40 ° C
Sample injection volume: 5 μL
・ Flow rate: 0.5mL / min
-Mobile phase solution A: 5 mM ammonium acetate aqueous solution
Liquid B: acetonitrile
Gradient (liquid B)
B liquid initial concentration: 20% (v / v)
20% → (7 minutes) → 20% → (10 minutes) → 95% → (5 minutes) → 95%
Analytical sample preparation: Prepared by diluting the reaction solution sampled in Examples 8 and 9 with methanol 300 times

The retention times of the respective compounds represented by the above formulas (α0), (α1A), (α1B), (α2) and (β0) to (β2) contained in the solutions sampled in Examples 8 and 9 are as follows. It was street.
Compound represented by formula (β0): retention time 13.5 to 14.2 minutes Compound represented by formula (β1): retention time 14.2 to 14.8 minutes Compound: Retention time 14.8 to 15.5 min. Compound represented by formula (α0): Retention time 15.5 to 16.2 min. Compound represented by formula (α1A) and (α1B): Retention Time 16.6 to 17.4 min. Compound represented by formula (α2): Retention time 18.1 to 19.3 min

  For the compounds represented by the above formulas (α0), (α1A), (α1B), (α2) and (β0) to (β2), the area ratio of each peak was calculated by the area percentage method by LC-MS. The dialkylation reaction rate and raw material consumption rate were calculated according to the formula. The results are shown in Table 1.

<Preparation of pigment dispersion>
Preparation Example 1
As a coloring agent, C.I. I. 12 parts by weight of Pigment Blue 15: 6, 12 parts by weight of BYK-LPN21116 (manufactured by BYK Corporation) as a dispersant (solid content concentration 40% by mass), binder resin (B1) solution (solid content concentration 40% by mass) Was treated with a bead mill using 12.5 parts by mass, 12 parts by mass of methoxypropanol and 51.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent to prepare a pigment dispersion (p-1).

<Preparation of colorant solution>
Preparation Example 2
10 parts by mass of the colorant (A-4) and 90 parts by mass of propylene glycol monomethyl ether were mixed to prepare a colorant solution (A-4).

Preparation Examples 3-11
In Preparation Example 2, the same procedures as in Preparation Example 2 were conducted except that colorants (A-5) to (A-10) and colorants (a1) to (a3) were used instead of colorant (A-4). Colorant solutions (A-5) to (A-10) and colorant solutions (a1) to (a3) were prepared.

<(B) Synthesis of binder resin>
Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 80 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 50 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 15 parts by mass of 2-hydroxyethyl methacrylate, 28 parts by mass of 2-ethylhexyl methacrylate, N- Mixing of 12 parts by weight of phenylmaleimide, 15 parts by weight of mono (2-acryloyloxyethyl) succinate, 20 parts by weight of propylene glycol monomethyl ether acetate, and 6 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) The solution was added dropwise over 2 hours, and polymerization was carried out for 1 hour while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 40% by mass). The obtained binder resin was Mw = 10,500 and Mn = 5,900. This binder resin is referred to as “binder resin (B1)”.

Synthesis example 5
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 (B2)”.

<Preparation of green coloring composition (G-1) used for transferability evaluation>
Preparation Example 12
As a coloring agent, C.I. I. 9.6 parts by mass of CI Pigment Green 58, C.I. I. 3.4 parts by weight of Pigment Yellow 138, 10.0 parts by weight of BYK-LPN21116 (manufactured by BYK Corporation) as a dispersant (solid content concentration: 40% by mass), a binder resin (B1) solution (solid content concentration of 40 masses) %) Was treated with a bead mill using 12.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent and a pigment dispersion (p-2) was prepared.
68.3 parts by mass of pigment dispersion (p-2), 6.3 parts by mass of binder resin (B2) solution (solid content concentration 33% by mass), pentaerythritol tetraacrylate (trade name Aronix M-, manufactured by Toagosei Co., Ltd.) 450) 8.5 parts by mass, polybasic acid-modified acrylic oligomer (manufactured by Toagosei Co., Ltd., trade name Aronix M-520) 2.1 parts by mass, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals) 1.1 parts by mass, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5 '-Tetraphenyl-1,2'-biimidazole (trade name B-CIM, manufactured by Hodogaya Chemical Co., Ltd.) 0.5 parts by mass, 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd.) 0.5 parts by mass, 2-mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.2 parts by mass, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -ON (BSF, trade name IRGAC
URE907) 0.3 part by mass, 0.05 part by mass of Megafac F-554 (manufactured by DIC Corporation), and propylene glycol monomethyl ether acetate are mixed to give a green colored composition (G- 1) was prepared.

<Preparation and evaluation of coloring composition>
Example 10
As a colorant, 33.2 parts by mass of a pigment dispersion (p-1) and 8.1 parts by mass of a colorant solution (A-4) and 0.3 parts by mass of Solvent Blue 70 (Oil Blue 5511 manufactured by Arimoto Chemical) Binder resin (B1) solution 10 parts by mass as a binder resin, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a polymerizable compound, light As a polymerization initiator, 2.8 parts by mass of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by BASF, trade name IRGACURE907), 2,4-diethylthioxanthone ( Nippon Kayaku Co., Ltd.) 1.4 parts by mass and Adeka Arcles NCI-831 (Co., Ltd.) ADEKA (0.07 parts by mass), 0.8% by mass of a 5% by mass propylene glycol monomethyl ether acetate solution of Megafac F-554 (manufactured by DIC Corporation) as a surfactant, and 25 parts by mass of propylene glycol monomethyl ether as a solvent. Parts and propylene glycol monomethyl ether acetate were mixed to prepare a colored composition (S-1) having a solid concentration of 16% by mass.

Evaluation of Luminance and Contrast Ratio The colored composition (S-1) was applied on a glass substrate using a spin coater, and then pre-baked on an 80 ° C. hot plate for 10 minutes to form a coating film. Three coating films having different film thicknesses were formed by the same operation while changing the rotation speed of the spin coater.
Next, after cooling these substrates to room temperature, using a high-pressure mercury lamp, each coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at 600 J / m ² and an illuminance of 35 mW without using a photomask. Exposed in quantity. Then, shower development was performed for 50 seconds by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, these substrates were washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 30 minutes to form a blue cured film.
Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) for the three cured films obtained, Bx = 0.140 and By = 0.098 in the CIE color system with a C light source and a 2-degree field of view. The stimulation value (Y) was measured.

  Further, the substrate on which the cured film is formed is sandwiched between two deflecting plates, and the front side deflecting plate is rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and the luminance meter LS-100 (Minolta) The maximum value and the minimum value of the transmitted light intensity were measured. And about each cured film, the value which remove | divided the maximum value by the minimum value was made into the contrast ratio. From the measurement result, the contrast ratio at the chromaticity coordinate value y = 0.098 was obtained. The evaluation results are shown in Table 2. Note that the larger the numerical value, the better the contrast ratio.

Evaluation of heat resistance After the substrate prepared for luminance evaluation was post-baked in a clean oven at 230 ° C for 75 minutes, the chromaticity coordinate values (x, y) and stimulus values (Y) were measured, and before and after additional baking. The color change at δ, ie, ΔE ^* ab was evaluated. As a result, the case where ΔE ^* ab was less than 4.5 was evaluated as “◯”, the case where 4.5 or more and less than 5.0 was evaluated as “Δ”, and the case where 5.0 or more was evaluated as “×”. The evaluation results are shown in Table 2.

Evaluation of dye transferability After applying the green coloring composition (G-1) on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed using a spin coater, 90 ° C. Pre-baking was performed for 2 minutes on a hot plate to form a coating film having a thickness of 2.4 μm.
Next, after cooling this substrate to room temperature, the entire surface was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at a dose of 400 J / m ² without using a photomask using a high-pressure mercury lamp. . Then, shower development was performed for 50 seconds by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 30 minutes to form a green cured film (T-1) on the substrate.
After the coloring composition (S-1) is applied on the green cured film (T-1) using a spin coater, it is pre-baked for 2 minutes on a 90 ° C. hot plate to form a coating film having a thickness of 3.0 μm. Formed. Next, after cooling the substrate to room temperature, a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. is discharged to the substrate at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm). Then, shower development was performed for 50 seconds. Thereafter, the substrate was washed with ultrapure water and air-dried. The process from applying the colored composition (S-1) on the green cured film (T-1) to air drying is referred to as (process-1).
(Step-1) The chromaticity coordinate value (x, y) and the stimulus value (Y) of the green cured film (T-1) are measured before and after, respectively, and the stimulus value change before and after (Step-1), that is, ΔE ^*. ab was evaluated. As a result, the case where the value of ΔE ^* ab was less than 0.5 was evaluated as “◯”, the case of 0.5 or more and less than 0.7 was evaluated as “Δ”, and the case of 0.7 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 is, the more the dye transfer property is suppressed.

Examples 11-16 and Comparative Examples 4-6
In Example 10, the amount of the pigment dispersion (p-1) and the kind and amount of the colorant solution were changed as shown in Table 2, and the same colored composition (S-2) as in Example 10. To (S-10) were prepared. And evaluation of brightness | luminance, heat resistance, and transferability was carried out similarly to Example 10 except having replaced with the coloring composition (S-1) and having used the coloring compositions (S-2)-(S-10). Went. The evaluation results are shown in Table 2.

Claims (7)

A coloring composition containing (A) a colorant, (B) a binder resin, and (C) a polymerizable compound,
(A) A coloring composition containing a compound represented by the following formula (1) as a coloring agent.

[In Formula (1),
R ^{1 to} R ⁴ and R ⁷ each independently represent a monovalent group.
R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent group, provided that at least one of R ⁵ and R ⁶ represents a monovalent group.
Z ^{a +} represents an a-valent onium cation.
a represents an integer of 1 or more.
b represents an integer of 1 or more determined so that the compound represented by the formula (1) is electrically neutral. When b is 2 or more, a plurality of (Z ^{a +} ) may be the same or different. Also good.
x shows the integer of 0-5.
y and z each independently represent an integer of 0 to 3.
However, two or more of R ^{1 to} R ⁷ are —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^— , or one having —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^—. Is a valent group. ] The coloring composition according to claim 1, wherein (Z ^{a +} ) is an ammonium cation, a phosphonium cation, a resin having an ammonium base, or a resin having a phosphonium base. x is 1,
R ¹ is —CO ₂ ^— or —SO ₃ ^— ;
y and z are 0,
R ⁴ is a substituted or unsubstituted aromatic hydrocarbon group,
R ⁷ is an aromatic hydrocarbon group having —SO ₃ ^— as a substituent,
R ⁵ and R ⁶ are each independently a substituted or unsubstituted aliphatic hydrocarbon group,
The coloring composition according to claim 1 or 2. The colored cured film containing the compound represented by following formula (1).

[In Formula (1),
R ^{1 to} R ⁴ and R ⁷ each independently represent a monovalent group.
R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent group, provided that at least one of R ⁵ and R ⁶ represents a monovalent group.
Z ^{a +} represents an a-valent onium cation.
a represents an integer of 1 or more.
b represents an integer of 1 or more determined so that the compound represented by the formula (1) is electrically neutral. When b is 2 or more, a plurality of (Z ^{a +} ) may be the same or different. Also good.
x shows the integer of 0-5.
y and z each independently represent an integer of 0 to 3.
However, two or more of R ^{1 to} R ⁷ are —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^— , or one having —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^—. Is a valent group. ]   A display element comprising the colored cured film according to claim 4. It has a structure represented by the following formula (102) including a step of reacting a compound having the structure represented by the following formula (100) with a compound represented by the following formula (101) in the presence of a base. Compound production method.

[In Formula (100),
R ^{1 to} R ⁴ and R ⁷ each independently represent a monovalent group.
x shows the integer of 0-5.
y and z each independently represent an integer of 0 to 3.
Provided that at least two of R ^{1 to} R ⁴ and R ⁷ are —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^— , or —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^—. It is a monovalent group having ]

[In Formula (101),
R represents a monovalent hydrocarbon group.
X represents Br, I or OT _f .
_Tf represents a trifluoromethylsulfonyl group. ]

[In Formula (102),
R ^{1 to} R ⁴ , R ⁷ , R, x, y, and z are as defined above. ] A compound represented by the following formula (1).

[In Formula (1),
R ^{1 to} R ⁴ and R ⁷ each independently represent a monovalent group.
R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent group, provided that at least one of R ⁵ and R ⁶ represents a monovalent group.
Z ^{a +} represents an a-valent onium cation.
a represents an integer of 1 or more.
b represents an integer of 1 or more determined so that the compound represented by the formula (1) is electrically neutral. When b is 2 or more, a plurality of (Z ^{a +} ) may be the same or different. Also good.
x shows the integer of 0-5.
y and z each independently represent an integer of 0 to 3.
However, two or more of R ^{1 to} R ⁷ are —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^— , or one having —CO ₂ ^— , —SO ₃ ^— or —PO ₄ ^—. Is a valent group. ]