JP6511763B2 - Colored composition for color filter and color filter - Google Patents

Description

  The present invention relates to a photosensitive coloring composition used for producing a color filter used for a color liquid crystal display device, a color imaging tube device and the like, and a color filter provided with a filter segment formed using the same. .

In the liquid crystal display device, a liquid crystal substance and a pixel are interposed between two polarizing plates, a voltage is applied to each pixel to change the alignment state of the liquid crystal substance, and the degree of polarization of light passing through the first polarizing plate It is a display device which changes and displays the screen by controlling transmitted light passing through the second polarizing plate.
By providing a color filter between the two polarizing plates, color display becomes possible, and it can be used for televisions, personal computers, monitors and the like.

  A color filter is provided on a transparent substrate such as a glass plate to prevent color mixing of transmitted light and to increase a display contrast by providing a grid-like light shielding film black matrix (hereinafter referred to as BM). Green, blue) filter segments are provided. The filter segments are as fine as several microns to several hundred microns, and the arrangement of the filter segments may be arranged in the form of fine bands (stripes) of two or more different hues (stripe arrangement), or an arrangement of constant height and width There are those (delta arrangement) etc. which were arranged in. The filter segment and BM are generally coated with a photosensitive coloring composition, exposed to ultraviolet light, and formed dry at a high temperature of 200 ° C. or higher, preferably 230 ° C., after development with an alkali developer or the like.

  In the color liquid crystal display device, a transparent electrode for driving the liquid crystal is formed on the color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. . In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof needs to be carried out generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, a method called a pigment dispersion method in which a pigment having excellent heat resistance is used as a colorant is mainly used as a method for producing a color filter.

  In the pigment dispersion method, a color resist is formed by mixing and preparing a photosensitive agent, an additive and the like in a resin in which pigment particles as a colorant are dispersed, and this color resist is coated on a substrate such as a spin coater. This is a method of forming a coating film, selectively exposing through a mask with an aligner, a stepper or the like, patterning by performing alkali development and thermosetting treatment, and repeating this operation to produce a color filter.

  In recent years, in order to realize a high contrast ratio and a high lightness that can not be achieved with a pigment, a technology using a dye as a coloring agent has been proposed as in Patent Document 1. However, if only dyes such as direct dyes and acid dyes are used, as in Patent Document 2, although color developability is good, heat resistance and light resistance tend to be poor. Therefore, in the use of dyes, there is a need for a solution to the technical problem that both fastness and color characteristics are compatible and that the stability of the coloring composition is also excellent.

Japanese Patent Application Laid-Open No. 6-75375 JP-A-8-327811

  The present invention has been made in view of the above-mentioned present situation, and is a high stability, color composition for color filters which is excellent in fastness such as heat resistance and chemical resistance while having high brightness, and use thereof It is an object of the present invention to provide a color filter having good color characteristics and excellent fastness.

  As a result of intensive studies to solve the above problems, the present inventors have studied cyanine dyes (ZC) represented by the general formula (1) and an organic solvent (D1) having a hydroxyl group having a specific content. It has been found that the above-mentioned problems are solved by the coloring composition for a color filter containing

That is, the present invention is a coloring composition for a color filter containing a colorant, a binder resin, and an organic solvent (D), wherein the colorant is a cyanine dye (ZC) represented by the following general formula (1): Contains
The organic solvent (D) contains an organic solvent (D1) having a hydroxyl group, and the content of the organic solvent (D1) having a hydroxyl group is 10% by weight or more in the total 100% by weight of the organic solvent (D) The present invention relates to a coloring composition for a color filter characterized by
[In the general formula (1),
A represents a carbon atom having a substituent or a hydrogen atom, or a sulfur atom.
R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, a substituted or no substituent It represents a substituted aryl group or a substituted or unsubstituted acyl group.
R ¹¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a halogen atom.
R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
Y ^- represents an inorganic or organic anion.
However, this is excluded when Y ^- is a halide ion. ]

Further, the present invention, Y ^- an anion represented is represented by the imide anion represented by the following general formula (2), fluorine-containing boron anion represented by the following general formula (3), the following general formula (4) The present invention relates to the coloring composition for a color filter, which is at least one selected from the group consisting of a methide acid anion and a vinyl resin having a structural unit represented by the following general formula (5).
[In the general formula (2),
R ²¹ and R ²² are each independently an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or aromatic carbonization which may have a substituent Represents a hydrogen group or a heterocyclic group which may have a substituent. ]
[In the general formula (3),
R ^{31 to} R ³⁴ each independently represent an alkyl group which may be substituted by a fluorine atom, a cyano group, a hydrogen atom, a fluorine atom or an aryl group which may be substituted by a fluorine atom,
At least one of R ^{31 to} R ^{34 represents} an alkyl group which may be substituted with a fluorine atom, a fluorine atom, or an aryl group which may be substituted with a fluorine atom.
However, the case where all of R ^{31 to} R ³⁴ are fluorine atoms is excluded. ]
[In the general formula (4),
Each of R ^{41 to} R ⁴³ independently represents an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. ]
[In the general formula (5),
R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
Q represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, -CONH-R ^52- , or -COO-R ^52- ,
R ⁵² represents a substituted or unsubstituted alkylene group.
P ^- is, -SO ₃ ^-, or -COO ^- represents a. ]

The present invention also relates to the coloring composition for a color filter, wherein the solubility parameter (SP value) of the organic solvent (D1) is 16 MPa ^1/2 or more and less than 24 MPa ^1/2 .

  The present invention also relates to the coloring composition for color filters, wherein the organic solvent (D1) has a ketone group or an ester group.

  The present invention also relates to the coloring composition for color filters, wherein the organic solvent (D1) is ethyl lactate.

  Further, the present invention relates to the coloring composition for color filter, which further comprises a photopolymerization initiator.

The present invention also relates to a color filter comprising a filter segment formed from the coloring composition for color filter on a substrate.
Related to

  The color composition for color filters of the present invention is excellent in fastness such as heat resistance and chemical resistance while being high in brightness, and can form a filter segment excellent in color characteristics and also in stability. Thereby, high quality color filters can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
In addition, in this specification, when it describes with "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide", Unless otherwise stated, respectively, "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide" It represents ".
In addition, “CI” listed in the present specification means a color index (CI).

The coloring composition for color filter of the present invention contains a colorant, a binder resin, and an organic solvent (D), and the colorant contains a cyanine dye (ZC) represented by the following general formula (1),
The organic solvent (D) contains an organic solvent (D1) having a hydroxyl group, and the content of the organic solvent (D1) having a hydroxyl group is 10% by weight or more in the total 100% by weight of the organic solvent (D) It is.
First, various components of the coloring composition for color filter of the present invention will be described.

<Colorant>
The coloring composition for color filters of the present invention contains a cyanine dye (ZC) represented by General Formula (1) as a colorant.

  In the coloring composition for a color filter of the present invention, the colorant concentration relative to all nonvolatile components is preferably 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of obtaining sufficient color reproducibility. Most preferably, it is 20 to 80% by weight. If the concentration of the colorant component is 10% by weight or more, sufficient color reproducibility can be obtained, and if it is 90% by weight or less, the concentration of the colorant carrier such as the binder resin becomes sufficient, and the coloring composition The stability of the object is good.

(Cyanine Dye (ZC) Represented by General Formula (1))
The cyanine dye of the present invention has a structure in which a cation site and an anion site are salt-formed as represented by the general formula (1), and the cation site is a cationic cyanine dye represented by the general formula (1-2) The anion site is an inorganic or organic anion other than a halide ion. In particular, in the cyanine dye of the present invention, a salt forming compound of a cationic cyanine dye represented by the general formula (1-2) and an anion represented by the general formula (2), (3) or (4) Is desirable. Alternatively, a salt forming compound with a vinyl resin having a structural unit represented by the general formula (5) is preferable in order to obtain excellent color characteristics and resistance.

[In the general formula (1), A represents a carbon atom having a substituent or a hydrogen atom, or a sulfur atom.
R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, a substituted or no substituent It represents a substituted aryl group or a substituted or unsubstituted acyl group.
R ¹¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a halogen atom.
R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
Y ^- represents an inorganic or organic anion.
However, this is excluded when Y ^- is a halide ion. ]

«Cationic Cyanine Dye»
[Cationic Cyanine Dye Represented by General Formula (1-2)]
The cationic cyanine dye of the present invention is a compound having a cation represented by the following general formula (1-2).

[In the general formula (1-2),
A represents a carbon atom having a substituent or a hydrogen atom, or a sulfur atom.
R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, a substituted or no substituent It represents a substituted aryl group or a substituted or unsubstituted acyl group.
R ¹¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a halogen atom.
R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. ]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like.
Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

  Examples of the aryl group include phenyl group, biphenylyl group, terphenylyl group, tetraphenylyl group, pentalenyl group, indenyl group, naphthyl group, binaphthalenyl group, ternaphthalenyl group, quarternaphthalenyl group, azulenyl group, heptalenyl group, biphenylenyl group, indasenyl group Group, fluoranthenyl group, acephenanthrylenyl group, aceanthrenyl group, phenarenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group Group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexene group Seniru group, rubicenyl group, coronenyl groups, trinaphthylenyl groups, heptacenyl groups, pyranthrenyl groups, there is ovalenyl group.

  These aryl groups may have a substituent. As a substituent in this case, a C1-C4 alkyl group, a C1-C4 alkoxy group, and an aryl group are mentioned.

  Examples of the acyl group include an acetyl group, an ethanolyl group, a propanoyl group, an isopropanoyl group, a butanoyl group, an isobutanoyl group, a sec-butanoyl group, a tert-butanoyl group and the like.

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

The organic group having a polymerizable functional group as referred to in the present invention is composed of an atomic group containing a polymerizable functional group, containing a carbon atom-hydrogen atom bond as a whole, and optionally containing an atom other than carbon Group is shown. Specifically, it may be composed of only a polymerizable functional group, or may be composed of a polymerizable functional group and a linking group.
Here, as a polymerizable functional group, a (meth) acryloyl group, a vinyl group, an epoxy group, an isocyanate group etc. are mentioned.
Further, as a linking group (as viewed from the cyanine skeleton), an alkylene group (hereinafter referred to as -X-), -XO- group, -XNH- group, arylene group, arylene oxy group, -XCONH- group,- XCOO- group, -XOCO- group, -XCOOX- group, -XOCOX- group, -XCOOXCOO- group, -XOCOXCOO- group, etc. may be mentioned.
Specific examples of the organic group having a polymerizable functional group are as shown in the following table (DC-5 to 8 and the like).

A carbon atom and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ¹² , A carbon atom and R ¹⁰ , R ⁹ and R ¹⁰ , R ⁸ and R ⁹ , R ⁷ and R ⁸ , and R ⁷ and R ¹³ may independently and / or simultaneously form an aliphatic saturated hydrocarbon or aromatic cyclic structure.

Specific examples of the cationic cyanine dye include the following cationic cyanine dyes and the like, but the present invention is not limited thereto. Also, when performing the salt formation, the counter of the cationic cyanine dyes shown below (DC-1~DC-91) is a halide ion, Cl ^- or Br ^- or I ^- is.

«Anion Y ^-»
In the general formula (1), Y ^- represents an inorganic or organic anion, as long as it has an anionic ion, either can be used. However, it excludes when it is a halide ion (Cl ^- etc).

Typical examples, triflate ion (CF ₃ SO ₃ ^-), benzoate ^{_{(C 6 H 5 COO -)}} , oxalate ion (C ^₂ O ₄ ^2-), perhalogen acid ion (ClO ₄ ^{-, _{FO 4 -, BrO 4 -,}} IO 4 - , etc.), thiocyanate ion (SCN ^-, etc.), sulfate ion (SO ₄ ^2-, HSO ₄ ^-, etc.), heteropolyacids, organic carboxylate ion, organic sulfonate ion (e.g. Alkyl sulfonate having 1 to 20 carbon atoms, benzene sulfonate, etc., fatty acid ion (such as aliphatic carboxylate having 1 to 20 carbon atoms), sulfonic acid group-containing nitrogen anion, fluorine group-containing boron anion, methide acid anion, fluorine group containing Phosphoric anion, cyano group-containing nitrogen anion, anion having conjugated base of organic acid having halogenated hydrocarbon group, acid dye, etc. It is, if these anions, there is no problem in resistance and color properties, can be preferably used.

These anions Y ^- Among, from the viewpoint of heat resistance, a sulfate ion, organic sulfonate ion, a sulfonic acid group-containing nitrogen anion, fluorine-containing boron anion or methide anion, preferably, organic sulfonate ions, containing a sulfonic acid group A nitrogen anion, a fluorine group-containing boron anion, or a methide acid anion is more preferable, and a sulfonic acid group-containing nitrogen anion, a fluorine group-containing boron anion, or a methide acid anion is particularly preferable.

  Further, among the sulfonic acid group-containing nitrogen anions, among the imidate anions represented by the general formula (2) and the fluorine group-containing boron anions, the fluorine group-containing boron anions represented by the general formula (3) and the methide acid anion Among them, the methide acid anion represented by the general formula (4) is the most preferable.

Or, it is also possible to use a resin having these anionic groups in the side chain, among such resins, anion site, -SO ₃ ^-, or -COO ^- preferably resins are, particularly preferably, It is a vinyl resin having a structural unit represented by the general formula (5) described later in terms of heat resistance and color characteristics.

Specifically as these anions,
Examples of heteropoly acids include phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, lintungstomolybdic acid, phosphovanadomolybdic acid, lintungstomolybdic acid, phosphovanadomolybdic acid, phosphotungstomolybdic acid, phosphotungstic acid, Anions such as phosphomolybdic acid, silicotungstic acid, silicomolybdic acid and the like can be mentioned.

  Examples of the organic carboxylate ion include tetrachlorophthalic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, oleic acid, elaidic acid, erucic acid, nervonic acid, linoleic acid, gamolenic acid, arachidonic acid, α- Anions of anionic compounds such as linolenic acid, stearidonic acid, eicosapentaenoic acid, docosahexaenoic acid and the like can be mentioned.

  Preferred compounds as the organic sulfonate ion are methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, dodecyl sulfone Acid, hexadecanesulfonic acid, icosanesulfonic acid, benzenesulfonic acid 1-naphthalenesulfonic acid, 4-phenylaminobenzenesulfonic acid, 1-naphthylamine-4,8-disulfonic acid, 1-naphthylamine-3,8-disulfonic acid, 1-naphthylamine-5,7-disulfonic acid, 1-naphthylamine-3,6-disulfonic acid, 1-naphthylamine-3,6,8-trisulfonic acid, 2-naphthylamine-6,8-disulfonic acid, 2-naphthylamine -1, 6 Disulfonic acid, 2-naphthylamine-4,8-disulfonic acid, 2-naphthylamine-3,6-disulfonic acid (amino-R acid), 2-naphthylamine-5,7-disulfonic acid (amino J acid), 1-naphthol 4,8-disulfonic acid, 1-naphthol-3,8-disulfonic acid (ε acid), 1-naphthol-3,6-disulfonic acid, 1-naphthol-3,6,8-trisulfonic acid, 2- Naphthol-6,8-disulfonic acid, 2-naphthol-3,6-disulfonic acid (R acid), 2-naphthol-3,6,8-trisulfonic acid, N-phenyl-1-naphthylamine-8-sulfonic acid N-p-tolyl-1-naphthylamine-8-sulfonic acid, N-phenyl-1-naphthylamine-5-sulfonic acid, N-phenyl-2-naphthylamine-6-sulfonic acid, N-acetyl-7-amino-1-naphthol-3-sulfonic acid, N-phenyl-7-amino-1-naphthol-3-sulfonic acid, N-acetyl-6-amino-1-naphthol-3-sulfonic acid N-phenyl-6-amino-1-naphthol-3-sulfonic acid, 1,8-dihydro-3,6-disulfonic acid (chromotropic acid), 8-amino-1-naphthol-3,6-disulfonic acid 8-amino-1-naphthol-5,7-disulfonic acid, 1,6-diamino-2-naphthol-4-sulfonic acid, 1-amino-2-naphthol-6,8-disulfonic acid, 1-amino- 2-naphthol-3,6-disulfonic acid, 2,8-diamino-1-naphthol-5,7-disulfonic acid, 2,7-diamino-1-naphthol-3-sulfonic acid, 2,6-diamino acid Anion of anionic compounds such as 1-naphthol-3-sulfonic acid, 2,8-diamino-1-naphthol-3,6-disulfonic acid, 2-amino-7-phenylamino-1-naphthol-3-sulfonic acid Can be mentioned.

  Anthracenesulfonic acid, anthraquinone-2-sulfonic acid, anthraquinone-1-sulfonic acid, 2-amino-1-naphthalenesulfonic acid (tobias acid), 4-amino-1-naphthalenesulfonic acid (naphthyonic acid), 8-amino acid -1-naphthalenesulfonic acid (peri acid), 2-amino-6-naphthalenesulfonic acid (brennaric acid), 1-amino-5-naphthalenesulfonic acid (lorentzic acid), 5-amino-2-naphthalenesulfonic acid (molecular weight 223) Anions of anionic compounds such as 1-amino-6-naphthalenesulfonic acid, 6-amino-1-naphthalenesulfonic acid, 3-amino-1-naphthalenesulfonic acid can also be used.

  Examples of fatty acid ions include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, cerotic acid, decilenic acid, dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid, petroselinic acid, vacenic acid, linoleic acid and eleostearin. Examples include anions of anionic compounds such as acid, lycoic acid, palinaric acid, taliphosphoric acid, gaderic acid, cetreic acid and ceracholeic acid.

As a sulfonic acid group-containing nitrogen anion, trifluoromethanesulfonamide anion, N- (trimethylsilyl) trifluoromethanesulfonamide anion, N- (2-methoxyethyl) trifluoromethanesulfonamide anion, p-trifluoromethylbenzenesulfonamide anion Others include sulfonylimidate anions.
Among these, from the viewpoint of heat resistance, sulfonylimidate anions are preferable, and imide acid anions represented by General Formula (2) described later are particularly preferable.

Examples of the fluorine group-containing boron anion include BF ₄ ⁻ or a fluorine group-containing boron anion represented by the general formula (3).
Among these, in view of heat resistance, a fluorine group-containing boron anion represented by General Formula (3) described later is particularly preferable.

As the fluorine group-containing phosphorus anion, PF ₆ ⁻ , (CF ₃ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) ₂ PF ₄ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CF] ₃ PF ₃ ⁻ , (nC ₃ F ₇ ) ₂ PF ₄ ⁻ , (nC ₃ F ₇ ) ₃ PF ₃ ⁻ , (nC _{4) ^{F 9) 3 PF 3 -,}} (C 2 F 5) (CF 3) 2 PF 3 -, [(CF 3) 2 CFCF 2] 2 PF 4 -, [(CF 3) 2 CFCF 2] 3 PF 3 - _{, (n-C 4 F 9} ) 2 PF 4 -, (n-C 4 F 9) 3 PF 3 -, (C 2 F 4 H) (CF 3) 2 PF 3 -, (C 2 F 3 H 2 ^{_{) 3 PF 3 -, (C}} 2 F 5) (CF 3) 2 PF 3 - , and the like.
Among these, PF ₆ ⁻ , (C ₂ F ₅ ) ₂ PF ₄ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , ((nC ₃ F ₇ ) ₃ PF ₃ ⁻ , (nC _{4) ^{F 9) 3 PF 3 -,}} [(CF 3) 2 CF] 3 PF 3 -, [(CF 3) 2 CF] 2 PF 4 -, [(CF 3) 2 CFCF 2] 3 PF 3 -, [( CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ^- is preferred.

As the cyano group-containing nitrogen anion, [(CN) ₂ N] ⁻ , [(FSO ₂ ) ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ SO ₂ )] ⁻ , [(FSO ₂ ) N (CF) ₃ CF ₂ SO ₂ ) ^- , [(FSO ₂ ) N {(CF ₃ ) ₂ CFSO ₂ }] ^- , [(FSO ₂ ) N (CF ₃ CF ₂ CF ₂ SO ₂ )] ^- , [(FSO ₂₎ ) N (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ )] ^- , [(FSO ₂ ) N {(CF ₃ ) ₂ CFCF ₂ SO ₂ }] ^- , [(FSO ₂ ) N {CF ₃ CF ₂ (CF ₃ ) CFSO ₂ }] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₃ CSO ₂ }] ^{−, and the} like.

The conjugate base of the organic acid having a halogenated hydrocarbon group is not particularly limited, but as the organic acid having a halogenated hydrocarbon group, for example, a sulfonic acid having a halogenated hydrocarbon group (-SO ₃ H), sulfonimidic acid (-SO ₂ NHSO _2- ) and the like can be mentioned.

Examples of the acid dyes include anthraquinone acid dyes, monoazo acid dyes, disazo acid dyes, oxazine acid dyes, aminoketone acid dyes, quinoline acid dyes, triarylmethane acid dyes and the like.
The hue can also be controlled by using an acid dye.

  Among them, in the present invention, the imidate anion represented by the general formula (2), the fluorine group-containing boron anion represented by the general formula (3), the methide acid anion represented by the general formula (4), and the general formula (5) It is desirable in terms of heat resistance and color characteristics to use any one of vinyl resins having a structural unit represented by

[Imidate anion represented by the general formula (2)]
[In the general formula (2),
R ²¹ and R ²² are each independently an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or aromatic carbonization which may have a substituent Represents a hydrogen group or a heterocyclic group which may have a substituent. ]

In the general formula (2), examples of the “aliphatic hydrocarbon group” include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and a dodecyl group. , Linear alkyl groups such as tridecyl group, pentadecyl group, hexadecyl group, octadecyl group, nonadecyl group and pentadecyl group; branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and isooctyl group And the like.
In the general formula (2), examples of the "alicyclic hydrocarbon group" include cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group and the like. Be
In the general formula (2), examples of the "aromatic hydrocarbon group" include a phenyl group, a biphenylyl group and a naphthyl group.

  In the general formula (2), as the “heterocyclic group”, indole ring, benzoindole ring, indolenine ring, benzoindolenine ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, benzoimidazole ring, quinoline Rings, etc. can be mentioned.

Further, R ²¹ and R ²² may form an aliphatic saturated hydrocarbon cyclic structure.

  In the general formula (2), examples of the “substituent” include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and isopentyl groups, Aliphatic hydrocarbon groups such as neopentyl group, tert-pentyl group, etc .; (meth) acryloyl group, vinyl aryl group, vinyl oxy group, allyl group, polymerizable groups such as epoxy group; phenyl group, o-tolyl group, m- Aromatic hydrocarbon groups such as tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group and the like; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy Alkoxy groups such as isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group; phenoxy Aryloxy group such as benzyloxy group; aralkyloxy group such as benzyloxy group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, group having an ester bond such as acetoxy group, benzoyloxy group; methylsulfamoyl group, dimethylsulfa group Moyl, ethylsulfamoyl, diethylsulfamoyl, n-propylsulfamoyl, di-n-propylsulfamoyl, isopropylsulfamoyl, diisopropylsulfamoyl, n-butylsulfayl Alkylsulfamoyl groups such as moyl group and di-n-butylsulfamoyl group; methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butyl Honiru group, tert- alkylsulfonyl group such as butyl sulfonyl group; can be nitro group, a cyano group and the like; fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom.

In the general formula (2), R ²¹ is an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or an aromatic which may have a substituent It is preferably a hydrocarbon group, and R ²² is preferably an aromatic hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent.

Among the above, R ^{21 in} General Formula (2) is preferably a fluorine atom-substituted alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group, and a fluorine atom-substituted group having 1 to 20 carbon atoms is preferable. An alkyl group is more preferable, and a trifluoromethyl group is particularly preferable.

Among the above, R ^{22 in the} general formula (2) is preferably a fluorine atom-substituted aromatic hydrocarbon group, more preferably a p-fluorophenyl group or a pentafluorophenyl group.

Specific examples of the imide acid anion include the following imide acid anions and the like, but the present invention is not limited thereto. Moreover, l and n show the integer of 1-5. In addition, when performing salt formation, the counter of the anionic compound which has the imide acid anion (IC-1-IC-59) shown below is Na ^<+> or K ^<+> or tetrabutyl ammonium or trimethyl ammonium.

[Fluorine group-containing boron anion represented by the general formula (3)]
[In the general formula (3),
R ^{31 to} R ³⁴ each independently represent an alkyl group which may be substituted by a fluorine atom, a cyano group, a hydrogen atom, a fluorine atom or an aryl group which may be substituted by a fluorine atom,
At least one of R ^{31 to} R ^{34 represents} an alkyl group which may be substituted with a fluorine atom, a fluorine atom, or an aryl group which may be substituted with a fluorine atom.
However, the case where all of R ^{31 to} R ³⁴ are fluorine atoms is excluded. ]

In the general formula (3), examples of the alkyl group represented by R ^{31 to} R ³⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group, A pentyl group, a hexyl group, an octyl group, an isooctyl group, a decyl group, a dodecyl group, a pentadecyl group and an octadecyl group may be mentioned and may be substituted by a fluorine atom. Examples of the alkyl group substituted by a fluorine atom include trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group and perfluorooctyl group.
The alkyl group preferably has 1 to 20 carbon atoms, and more preferably 2 to 18 carbon atoms, from the viewpoint of solubility in organic solvents, lightness, heat resistance, and contrast ratio. Is more preferred.

In the general formula (3), as the aryl group represented by R ^{31 to} R ³⁴ , a group containing a benzene ring, a group containing a condensed ring having aromaticity, a condensation having two or more benzene rings or aromaticity Included are groups having a structure in which rings are directly bonded, and groups in which two or more benzene rings or condensed rings having aromaticity are bonded via a group such as vinylene. The carbon number of the aryl group is preferably 6 to 60, and more preferably 6 to 30. Examples of the aryl group substituted by a fluorine atom include a phenyl group which may have a fluorine group, a 1-naphthyl group which may have a fluorine group, and a fluorine group 2 -A naphthyl group is mentioned. It is preferable that a fluorine atom is contained as a substituent from the viewpoint of heat resistance, lightness and contrast ratio.

Specifically, as the fluorine group-containing boron anion represented by the general formula (3), (CF ₃ ) ₄ B ⁻ , (CF ₃ ) ₃ BF ⁻ , (CF ₃ ) ₂ BF ₂ ⁻ , (CF ₃ ) BF ₃ ⁻ , (C ₂ F ₅ ) ₄ B ⁻ , (C ₂ F ₅ ) ₃ BF ⁻ , (C ₂ F ₅ ) BF ₃ ⁻ , (C ₂ F ₅ ) ₂ BF ₂ ⁻ , (CF ₃ ) (C ₂ ) F ₅ ) ₂ BF ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ , (CF ₃ C ₆ H ₄ ) ₄ B ⁻ , (C ₆ F ₅ ) ^{_{2 BF 2 -, (C 6}} F 5) BF 3 -, (C 6 H 3 F 2) 4 B -, B (CN) 4 -, B (CN) F 3 -, B (CN) 2 F 2 - ^{_{, B (CN) 3 F -}} , (CF 3) 3 B (CN) -, (CF 3) 2 B (CN) 2 -, (C 2 F 5) 3 B (CN) -, (C 2 F 5 ^{_{) 2 B (CN) 2 -}} , (n-C 3 F 7) 3 B (CN) -, (n-C 4 F 9) 3 B (CN) -, (n-C 4 _{F 9) 2 B (CN)} 2 -, (n-C 6 F 3) 3 B (CN) -, (CHF 2) 3 B (CN) -, (CHF 2) 2 B (CN) 2 -, ( CH ₂ CF ₃ ) ₃ B (CN) ⁻ , (CH ₂ CF ₃ ) ₂ B (CN) ₂ ⁻ , (CH ₂ C ₂ F ₅ ) ₃ B (CN) ⁻ , (CH ₂ C ₂ F ₅ ) _{2 ^{B (CN) 2 -, (}} CH 2 CH 2 C 3 F 7) 2 B (CN) 2 -, (n-C 3 F 7 CH 2) 2 B (CN) 2 -, (C 6 H 5) 3 B (CN) ^-, and the like.
Among them, B (CN) ₃ F ⁻ , (CF ₃ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , and [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ are preferable.

Also, as in (C ₆ F ₅ ) ₄ B ⁻ or [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ , at least one of R ^{31 to} R ³⁴ in the general formula (3) is a general one. It is preferable that it is a structure represented by Formula (3-2).

[In the general formula (3-2),
R ³⁵ to R ³⁹ each independently represent a hydrogen atom or a fluorine atom.
However, the case where all of R ^{35 to} R ³⁹ are hydrogen atoms is excluded. ]

Examples of the substituent represented by General Formula (3-2) include pentafluorophenyl group (C ₆ F ₅ ), trifluorophenyl group (C ₆ H ₂ F ₃ ), tetrafluorophenyl group (C ₆ HF ₄₎ ), Trifluoromethylphenyl group (CF ₃ C ₆ H ₄ ), bis (trifluoromethyl) phenyl group ((CF ₃ ) ₂ C ₆ H ₃ ), pentafluoroethylphenyl group (CF ₂ CF ₃ C ₆ H ₄₎ ), Bis (pentafluoroethyl) phenyl group ((CF ₂ CF ₃ ) ₂ C ₆ H ₃ ), fluoro-trifluoromethylphenyl group (CF ₃ C ₆ H ₃ F), fluoro-bis (trifluoromethyl) phenyl Group ((CF ₃ ) ₂ C ₆ H ₂ F), fluoro-pentafluoroethylphenyl group (CF ₃ CF ₂ C ₆ H ₃ F), fluoro-bis (pentafluoroethyl) phenyl group ((CF ₃ CF) ₂ ) ₂ C ₆ H ₂ F) and the like.

That is, as the fluorine group-containing boron anion represented by the general formula (3), among them, from the viewpoints of lightness, heat resistance and color characteristics, (C ₆ F ₅ ) ₄ B ⁻ , [(C ₆ H ₅ ) B _{(C 6 F 5) 3]} -, [(C 6 H 5) 2 B (C 6 F 5) 2] -, [(C 6 H 5) 3 B (C 6 F 5)] -, [(C ₆ H ₅ ) B (C ₆ H ₃ (CF ₃ ) ₂ ) ₃ ] — and the like. Among them, (C ₆ F ₅ ) ₄ B ^- is preferable.

[Methide Acid Anion Represented by General Formula (4)]
[In the general formula (4),
Each of R ^{41 to} R ⁴³ independently represents an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. ]

In the general formula (4), examples of the “aliphatic hydrocarbon group” include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and dodecyl groups. , Linear alkyl groups such as tridecyl group, pentadecyl group, hexadecyl group, octadecyl group, nonadecyl group and pentadecyl group; branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and isooctyl group And cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group and the like.
In the general formula (4), examples of the “aromatic hydrocarbon group” include a phenyl group, a biphenylyl group and a naphthyl group.

  In the general formula (4), examples of the “substituent” include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and isopentyl groups, Aliphatic hydrocarbon groups such as neopentyl group, tert-pentyl group, etc .; (meth) acryloyl group, vinyl aryl group, vinyl oxy group, allyl group, polymerizable groups such as epoxy group; phenyl group, o-tolyl group, m- Aromatic hydrocarbon groups such as tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group and the like; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy Alkoxy groups such as isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group; phenoxy Aryloxy group such as benzyloxy group; aralkyloxy group such as benzyloxy group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, group having an ester bond such as acetoxy group, benzoyloxy group; methylsulfamoyl group, dimethylsulfa group Moyl, ethylsulfamoyl, diethylsulfamoyl, n-propylsulfamoyl, di-n-propylsulfamoyl, isopropylsulfamoyl, diisopropylsulfamoyl, n-butylsulfayl Alkylsulfamoyl groups such as moyl group and di-n-butylsulfamoyl group; methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butyl Honiru group, tert- alkylsulfonyl group such as butyl sulfonyl group; fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom; a nitro group, can be mentioned a cyano group.

Among them, a halogenated aliphatic hydrocarbon group and a halogenated aromatic hydrocarbon group are preferable as R ^{41 to} R ^{43 in} the general formula (4). Further, in view of availability, R ^{41 to} R ⁴³ are preferably identical.

  In the general formula (4), examples of the “halogenated aliphatic hydrocarbon group” include trifluoromethyl group, difluoromethyl group, monofluoromethyl group, dichloromethyl group, monochloromethyl group, dibromomethyl group, difluorochloromethyl Group, pentafluoroethyl group, tetrafluoroethyl group, trifluoroethyl group, trifluorochloroethyl group, difluoroethyl group, monofluoroethyl group, trifluoroiodoethyl group, heptafluoropropyl group, hexafluoropropyl group, pentafluoro group Propyl, tetrafluoropropyl, trifluoropropyl, difluoropropyl, monofluoropropyl, perfluorobutyl, perfluorohexyl, perfluorooctyl, perfluorooctylethyl, pentafu Oro group, heptafluoroisopropyl group, can be perfluoro-3-methylbutyl group, a perfluoro-3-methylhexyl group and the like exemplified.

  In the general formula (4), examples of the “halogenated aromatic hydrocarbon group” include a pentafluorophenyl group, a tetrafluorophenyl group, a trifluorophenyl group, a difluorophenyl group, a monofluorophenyl group, a fluorochlorophenyl group, and a fluorochlorophenyl group. There may be mentioned chlorophenyl group, trichlorophenyl group, dichlorophenyl group, monochlorophenyl group, bromophenyl group, iodophenyl group and difluorobromophenyl group.

Among R ^{41 to} R ^{43 in} the general formula (4), among the above, a C 1 to C 10 aliphatic hydrocarbon group or aromatic hydrocarbon group substituted by a fluorine atom is preferable, and is substituted by a fluorine atom An aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable, and a trifluoromethyl group is particularly preferable in terms of heat resistance.

Although the methide acid anion etc. which are shown below are mentioned as a specific example of a methide acid anion, this invention is not limited to these. In addition, when performing salt formation, the counter of the anionic compound which has the methide acid anion (MC-1-MC-26) shown below is Na ^<+> , K ^<+> , Cs ^<+> or tetrabutyl ammonium.

[Vinyl-Based Resin Having Structural Unit Represented by General Formula (5)]
When the anion Y 1 ^- is a resin having an anionic group in the side chain, it is possible to use a vinyl resin having an anionic group having a structural unit represented by the general formula (5) among them. It is preferable in point. Among them, acrylic resins are preferably used.

[In general formula (5),
R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
Q represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, -CONH-R ^52- , or -COO-R ^52- ,
R ⁵² represents a substituted or unsubstituted alkylene group.
P ^- is, -SO ₃ ^-, or -COO ^- represents a. ]

In the general formula (5), examples of the alkyl group for R ⁵¹ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group and a cyclohexyl group. Be As this alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ⁵¹ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group. Among the above, as R ⁵¹ , a hydrogen atom or a methyl group is most preferable.

P in the general formula (5) in ^- is, -SO ₃ ^- or -COO ^- represents, -SO ₃ from the viewpoint of heat resistance ^- is more preferable.

In the general formula (5), acrylic site and P ^- component of Q connecting the alkylene group, an arylene ^{group, -CONH-R 52 -, -} COO-R 52 - represents, but R ⁵² represents an alkylene group, Among them, -CONH-R ⁵² -and -COO-R ⁵² -are preferable from the viewpoint of the polymerizability and the availability.

In General Formula (5) which comprises the said resin, in the step of the cationic cyanine dye and the precursor before salt formation, a cation component exists as a counter ion. In this case, employable cations are inorganic or organic cations, and known ones can be adopted without limitation. Specifically, hydrogen, an alkali metal, an alkaline earth metal, an ammonium compound and the like can be mentioned. At that time, the alkali metal is preferably sodium or potassium, and the alkaline earth metal is preferably calcium or magnesium. In addition, an ammonium compound is NH ⁴⁺ or a compound in which the H is substituted with a hydrocarbon group or the like.

  In order to obtain a vinyl resin containing a structural unit represented by the following general formula (5), which is a preferred embodiment of the present invention, a method of copolymerizing a monomer having a sulfonic acid group and / or a carboxyl group as a monomer component Can be mentioned.

  Hereinafter, specific examples of the ethylenically unsaturated monomer having a sulfonic acid group or a carboxyl group that can be used to obtain a vinyl-based resin containing a structural unit represented by General Formula (5) will be shown.

"Carboxyl group-containing ethylenic unsaturated monomer"
Examples of the ethylenically unsaturated monomer having a carboxyl group include, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like, and examples of the monomer having a carboxyl group Also included are monomers having a carboxylic acid anhydride group, and examples of monomers having a carboxylic acid anhydride group include maleic anhydride and itaconic acid anhydride.

"Sulfonate-containing ethylenic unsaturated monomer"
Ethylenically unsaturated monomers having a sulfonic acid group are ethylenically unsaturated monomers of the formula (IV) and water-soluble salts thereof, in particular alkali metal salts such as potassium and very particularly preferably sodium salts. And ammonium salts.
Formula (IV)
^{R 56 (R 57) C =} C (R 58) -X-SO 3 H
[Wherein, R ⁵⁶ , R ⁵⁷ and R ⁵⁸ independently of each other represent —H, a linear or branched alkyl group having 1 to 12 C atoms, a linear or branched C atom 2 to 12 Mono- or poly-unsaturated alkenyl groups having the following (wherein the latter two groups are unsubstituted or substituted by one or more groups -NH ₂ , -OH or -COOH) , -COOH or -COOR ⁵⁹ , and R ⁵⁶ is XSO ₃ H; R ⁵⁹ is a saturated or unsaturated linear or branched hydrocarbon having 1 to 12 C atoms; X is , Single bond, n is 1 to 4 and-(CH ₂ ) n-, phenylene, preferably 1,4-phenylene, -CH ₂ -O-phenylene (preferably 1,4), -CH ₂ -O- _{CH 2 -CH (OH) -CH 2} -, is k = 1 to 6 -COO- ( _{CH 2) k -, - CO} -NH-, m = 0~3 a is -CO-NH-CR'R '' - (CH 2) m or _{-CO-NH-CH 2 -CH (} OH) -CH ₂ -; R 'is -H, a -CH ₃ or -C ₂ H ₅ and R''is -H or -CH _3. ]

Particularly preferred among the ethylenically unsaturated monomers having sulfonic acid groups are those of the formulas (IVa), (IVb) and / or (IVc).
_{H 2 C = CH-X-} SO 3 H (IVa)
_{H 2 C = C (CH 3} ) -X-SO 3 H (IVb)
^{_{HO 3 S-X- (R 500}} ) C = C (R 511) -X-SO 3 H (IVc)
[Wherein, R ⁵⁰⁰ and R ⁵¹¹ independently of one another are —H, —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ or —CH (CH ₃ ) ₂ and X is a single one A bond, n = 1 to 4-(CH ₂ ) n-, phenylene, preferably 1,4-phenylene, -CH ₂ -O-phenylene (preferably 1,4), -CH ₂ -O-CH _{2- CH (OH) -CH 2 -,} k = 1~6 of _{-COO- (CH 2) k -,} - CO-NH-, m = 0~3 of -CO-NH-CR'R '' - (CH ₂₎ m-or _{-CO-NH-CH 2 -CH (} OH) -CH 2 - and is; R 'is, -H, a -CH ₃ or -C ₂ H ₅ and R''are, -H Or -CH ₃ . ]

  Highly preferred sulfonic acid group-containing ethylenically unsaturated monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid Methyl-2-propene-1-sulfonic acid), allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, styrenesulfonic acid, p-styrenesulfonic acid , Vinyl sulfonic acid, isoprene sulfonic acid, 3-s Water-soluble salts and esters of the acids mentioned, wherein alkali metal salts and alkaline earths are used; Advantageously, they are in the form of metal salts, in particular in the form of Na and K salts.

  Particularly preferred ethylenically unsaturated monomers having sulfonic acid groups are 2-acrylamido-2-methyl-1-propanesulfonic acid, vinylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, or 2-sodium It is sulfoethyl methacrylate.

"Other copolymerizable ethylenically unsaturated monomers"
In addition, as an ethylenically unsaturated monomer which can be used, for example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (Meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable.

As specific examples of such ethylenically unsaturated monomers, the following compounds may, for example, be mentioned.
Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2- (meth) acrylate Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (Meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-ethoxyethyl (Meth) acrylic acid 2- (2-methoxyethoxy) ethyl, (meth) acrylic acid 3-phenoxy-2-hydroxypropyl, (meth) acrylic acid benzyl, (meth) acrylic acid diethylene glycol monomethyl ether, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( (Meth) acrylic acid β-phenoxyethoxyethyl, (meth) acrylic acid nonyl phenoxy polyethylene glycol, (meth) acrylic acid dicyclopentenyl, (meth) acrylic acid dicyclo Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And tribromophenyloxyethyl (meth) acrylate.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, and vinyl benzoate. Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

  Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-n -Butyl acrylic (meth) amide, N-t-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloyl morpholine, diacetone acrylamide and the like.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes are styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Styrene, hydroxystyrene protected with a deprotectable group by an acidic substance (for example, t-Boc and the like), methyl vinyl benzoate, and α-methylstyrene and the like can be mentioned.

  Methyl (meth) acrylate, lauryl (meth) acrylate, styrene, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate or benzyl (meth) acrylate is preferred, 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, lauryl (meth) acrylate or styrene are more preferable from the viewpoint of storage stability of a colored composition using a salt-forming compound.

"Other ethylenically unsaturated monomers containing copolymerizable thermally crosslinkable functional groups"
By copolymerizing an ethylenically unsaturated monomer containing a thermally crosslinkable functional group, in the heating step in the production of a color filter, acrylic resins having a thermally crosslinkable functional group are formed or crosslinked with a binder resin. . As a result, a strong coating is formed, which can prevent the color change of the coating, that is, the heat resistance can be improved, and the chemical resistance is also improved.

The preferred structure of the thermally crosslinkable functional group is not particularly limited, and examples thereof include a hydroxyl group, primary or secondary amino group, imino group, oxetanyl group, t-butyl group, epoxy group, mercapto group, isocyanate group, An allyl group, a (meth) acryl group, etc. are mentioned.
Among them, a hydroxyl group, an oxetanyl group, a t-butyl group, an isocyanate group and a (meth) acrylic group are preferable, and a hydroxyl group is particularly preferable, from the viewpoint of storage stability in the application of the coloring composition for color filter and reactivity with other materials. It is preferable to have

  One method for introducing a thermally crosslinkable functional group in a vinyl resin having an anionic group into a vinyl resin having an anionic group, which is used in the present invention, is: a single amount of ethylenically unsaturated monomer having a heat crosslinkable functional group This method is a method of copolymerizing a body with an ethylenically unsaturated monomer corresponding to the structural unit represented by the general formula (5).

  Examples of the ethylenically unsaturated monomer having a hydroxyl group include, but not limited to, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples thereof include glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, and caprolactone adducts of these monomers (the addition molar number is preferably 1 to 5).

  As an ethylenically unsaturated monomer having an oxetanyl group, 3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, 3- (methacryloyloxymethyl) 3-ethyl oxetane, 3- (acryloyloxymethyl) 3-butyl oxetane, 3- (methacryloyloxymethyl) 3-butyl oxetane, 3- (acryloyloxymethyl) 3-hexyl oxetane and 3- (Methacryloyloxymethyl) 3-hexyl oxetane and the like.

  Examples of the ethylenically unsaturated monomer having a t-butyl group include t-butyl acrylate and t-butyl methacrylate.

  As an ethylenic unsaturated monomer which has an isocyanate group, 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, 4-isocyanate butyl acrylate etc. are mentioned, for example.

  As the isocyanate group in the present invention, a blocked isocyanate group is also included and can be preferably used. With a blocked isocyanate group, under ordinary conditions, while the reactivity of the isocyanate group is suppressed by protecting the isocyanate group with another functional group, it can be deprotected by heating to regenerate an active isocyanate group. Indicates an isocyanate block.

  As a commercial item of the ethylenically unsaturated monomer which has such a block isocyanate group, for example, 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (Karenz MOI-BP, Showa Denko); Methacrylic acid 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl (Karenz MOI-BM, manufactured by Showa Denko K. K.) and the like can be mentioned.

  Moreover, as an ethylenically unsaturated monomer which has a block isocyanate group, besides using a commercial item, it can also prepare and use by a well-known method. For example, the isocyanate compound having an ethylenically unsaturated bond and the blocking agent are stirred in a solvent at a temperature of about 0 to 200 ° C., and known separation and purification means such as concentration, filtration, extraction, crystallization and distillation may be used. It can be obtained by separation using.

  Another method for introducing a thermally crosslinkable functional group in a vinyl resin having an anionic group used in the present invention is to obtain the vinyl resin and then to the functional group of the vinyl resin with respect to the functional group. It is a method of reacting a compound having a functional group capable of reacting and a thermally crosslinkable functional group. For example, an acrylic resin having a (meth) acryloyl group as a thermally crosslinkable functional group can be obtained by reacting a glycidyl group of an ethylenically unsaturated monomer having a glycidyl group with a carboxyl group in an acrylic resin having a carboxyl group. You can get it.

  The thermally crosslinkable functional group needs to be contained at least one type in the resin, and two or more types may be contained.

  As a method for obtaining a vinyl resin having a structural unit represented by the general formula (5) suitable for the present invention, anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, living radical polymerization, etc. , Known methods can be used. Among these, free radical polymerization or living radical polymerization is preferable.

  In the case of free radical polymerization, it is preferred to use a polymerization initiator. For example, an azo compound and an organic peroxide can be used as the polymerization initiator. Examples of the azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane 1-carbonitrile), 2 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methyl propionate) 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), or 2,2'-azobis [2- (2-imidazolin-2-yl) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxy dicarbonate, di-n-propyl peroxy dicarbonate, di (2-ethoxyethyl) peroxy Dicarbonate, t-butyl peroxy neodecanoate, t-butyl peroxy bivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, or diacetyl peroxide may, for example, be mentioned. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

  In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and further, since the growth of polymerization occurs uniformly, block polymers and resins with uniform molecular weight can be easily synthesized.

  Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer radical polymerization method can be performed by the method described in the following references 1 to 8 and the like.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 791, Science, 1996, 272, 866
(Reference 5) WO 96/030421
(Reference 6) WO 97/018247
(Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-41117

  It is preferable to use an organic solvent for the above polymerization. The organic solvent is not particularly limited. For example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, or diethylene glycol monobutyl ether acetate may, for example, be used. These polymerization solvents may be used as a mixture of two or more.

  The total of structural units having a sulfonic acid group and a carboxyl group present in the vinyl resin having a structural unit represented by the general formula (5) suitable for the present invention is 2 to 2% of the total 100% by weight of the copolymerization composition. It is preferably a copolymer containing 50% by weight, more preferably a copolymer containing 5 to 35% by weight. When the total of structural units having a sulfonic acid group and a carboxyl group is less than 2% by weight, the proportion of cationic dyes in which a salt forming reaction occurs is low. Therefore, the amount of unformed salt cationic dye is increased, and as a result, the solvent solubility may be lowered, and a phenomenon such as precipitation of foreign matter may occur. Further, in order to prevent the deposition of foreign matter, it is necessary to increase the amount of organic solvent in the resist material, but in such a case, the coatability may be significantly deteriorated. On the other hand, if it is more than 50% by weight, the amount of the cationic dye formed in the vinyl-based resin containing the structural unit represented by the general formula (5) will be too large, so the heat resistance may be deteriorated. is there.

  The molecular weight of the vinyl resin having a structural unit represented by the general formula (5) used in the present invention is not particularly limited, but the converted weight average molecular weight measured by gel permeation chromatography (GPC) is It is preferably 1,000 to 500,000, and more preferably 3,000 to 15,000.

  Moreover, it is preferable that the vinyl resin containing the structural unit represented by General formula (5) suitable for this invention has the characteristic melt | dissolved in the organic solvent widely used by the coloring composition for color filters. Thereby, a coating film free from the occurrence of foreign matter can be obtained. In particular, it is preferable to dissolve in glycol acetates, particularly propylene glycol monomethyl ether acetate.

[Salt formation of cationic cyanine dyes and anionic compounds]
In the salt forming compound of the present invention, an aqueous solution in which an anionic compound having the above-mentioned anion Y ⁻ and a cationic cyanine dye is stirred or vibrated, or an aqueous solution of the anionic compound and an aqueous solution of the cationic cyanine dye The salt forming compound can be easily obtained by mixing under agitation or vibration. In an aqueous solution, the anionic group of the anionic compound and the cationic group of the cationic cyanine dye are ionized, and these are ionically bound, and the ionically bonded portion becomes water insoluble and a salt-forming compound precipitates. On the contrary, since the salt consisting of the counter cation of an anionic compound and the counter anion of a cationic cyanine dye is water soluble, it can be removed by washing with water or the like. As the anionic compound and the cationic cyanine dye to be used, only a single type may be used or a plurality of types having different structures may be used.

  In addition, when the cationic cyanine dye or the anionic compound is insoluble in water, each is appropriately dissolved in a soluble organic solvent, heated and stirred, and then the organic solvent is distilled off under reduced pressure or normal pressure. Alternatively, a solid may be obtained, water may be added thereto and reslurrying may be carried out to remove a salt which is a by-product, and then the solid may be separated by filtration to obtain a salt forming compound. At this time, a water-soluble organic solvent described later can be used as the organic solvent to be used.

  The salt forming compound of the present invention is preferably a salt forming compound obtained by removing a salt composed of a counter cation of an anionic compound and a counter anion of a cationic cyanine dye from the viewpoint of heat resistance. When a salt forming compound contains a by-product (e.g., NaCl) generated by salt formation, the salt forming compound may be precipitated over time in the coloring composition.

  A mixed solution of water and a water-soluble organic solvent may be used to dissolve the anionic compound and the cationic cyanine dye as an aqueous solution used at the time of salt formation. As the water-soluble organic solvent, methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2- (methoxy methoxy) ethanol Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone, N, N -Dimethylformamide, dimethylsulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol, tetrahydrofurfuryl Alcohol, 4-methoxy-4 methyl pentanone, etc. are mentioned. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight, based on the total weight (100% by weight) of the aqueous solution.

  The ratio of the anionic compound to the cationic cyanine dye is such that the molar ratio of the anionic unit of the anionic compound to the total cationic group of the cationic cyanine dye is in the range of 10/1 to 1/4. The salt forming compound can be suitably adjusted, and the range of 2/1 to 1/2 is more preferable.

(Organic pigment (B))
An organic pigment (B) can also be used for the photosensitive coloring composition of this invention. This makes it possible to adjust the hue and improve the tolerance.
The content of the organic pigment (B) is preferably 0 to 300 parts by weight with respect to 100 parts by weight of the cyanine dye (ZC). More preferably, it is 50 to 200 parts by weight. When the addition amount of the cyanine dye (ZC) is in this range, the hue and the reproducible chromaticity range can also be an excellent composition.

As the pigment to be used in combination, the following ones are used for each filter segment of each color.
«Pigment which forms red filter segment»
As a red pigment for the red coloring composition which forms a red filter segment,
C. I. Pigment red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 149, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 224, 242, 246, 254, 255, 264, 268, 269, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, the diketopyrrolopyrrole pigment described in JP-A-2011-523433, or JP-A-2013 Although the naphthol azo pigment etc. which are described in the -161025 gazette etc. are mentioned, it is not limited in particular in these.
Among them, spectral characteristics excellent in color reproducibility and sensitivity can be obtained. I. It is preferable to use pigment red 177, 242, 254 or 269. More preferably, C.I. I. Pigment red 177 or 254.

  In addition, yellow or orange pigments may be used in combination to form a red filter segment. Examples of yellow or orange pigments include yellow pigments and orange pigments described below.

As yellow pigments, C.I. I. Pigment yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 181, 181, 181, 181, 82, 185, 187, 188, 193, 194, 198, 199, 199, 213, 214, 218, 219, 220, 221 or quinophthalone pigments described in Japanese Patent No. 499 3026, but not limited thereto .
As an orange pigment, C.I. I. Pigment orange 38, 43, 71, or 73, but not limited thereto.
Among them, spectral characteristics excellent in color reproducibility and sensitivity can be obtained. I. Pigment Yellow 138, 139, 150, or 185 is preferably used. More preferably, C.I. I. Pigment yellow 139.

  These organic pigments can be used alone or in combination of two or more in any ratio as required.

«Pigment forming blue filter segment»
As blue pigments for blue coloring compositions forming blue filter segments:
C. I. Pigment blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP-A-2004-333817, Alternatively, aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, etc. may be mentioned, but the invention is not particularly limited thereto.
As a purple pigment, C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, or 50, but is not particularly limited thereto.
Among them, spectral characteristics excellent in color reproducibility and sensitivity can be obtained. I. It is preferable to use pigment blue 15: 1 or 15: 6.

«Pigment which forms green filter segment»
As green pigments for green coloring compositions forming green filter segments:
C. I. Pigment greens 7, 10, 36, 37, 58, JP 2008-19383 A, JP 2007-320986 A, JP 2004 70342 A etc., or the zinc phthalocyanine pigment described in JP 4893 859 A etc. Although the aluminum phthalocyanine pigment as described in is mentioned, it is not limited to these in particular.
Among them, spectral characteristics excellent in color reproducibility and sensitivity can be obtained. I. It is preferable to use pigment green 7, 36 or 58.

  In addition, it is possible to use a yellow pigment in combination with the green coloring composition in order to adjust the hue.

As yellow pigments, C.I. I. Pigment yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 181, 181, 181, 181, 82, 185, 187, 188, 193, 194, 198, 199, 199, 213, 214, 218, 219, 220, 221, or quinophthalone pigments described in Japanese Patent No. 499 3026, and the like, but it is particularly limited thereto I will not.
Among them, spectral characteristics excellent in color reproducibility and sensitivity can be obtained. I. Pigment Yellow 138, 139, 150, or 185 is preferably used.

[Finening of pigment]
The organic pigment (B) of the present invention is preferably used after being finely divided. The method of refining is not particularly limited, and any of wet grinding, dry grinding and solution precipitation methods can be used, for example, and as exemplified in the present invention, salt milling treatment by kneader method which is one of wet grinding Etc. to be miniaturized. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. In addition, the thickness is preferably 100 nm or less because a filter segment having a high contrast ratio can be formed. The particularly preferred range is in the range of 25 to 85 nm. The primary particle diameter of the pigment was determined by a method of directly measuring the size of the primary particles from an electron micrograph of the pigment by a TEM (transmission electron microscope). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was defined as the particle size of the pigment particles.

  Salt milling treatment is a batch type or continuous type of kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. of a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent. After mechanically kneading while heating using a kneader, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and at the time of salt milling, the pigment is crushed using the hardness of the inorganic salt. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used in terms of price. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight, based on 100 parts by weight of the total weight of the pigment, from both the processing efficiency and the production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is easily evaporated, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the total weight of the pigment.

  When the pigment is subjected to salt milling, a resin may be added as necessary. The type of resin to be used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is preferably solid at room temperature, preferably water insoluble, and more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the total weight of the pigment.

  It is also preferable to add the cyanine dye (ZC) of the present invention at the same time as the salt milling (refinement) of the pigment. When the pigment is refined, it can be made a good colorant by adding it together.

(Other coloring agents)
The coloring composition for solid-state imaging devices of the present invention may further be used in combination with other dyes.
Examples of dyes that can be used in combination include compounds classified as dyes according to Color Index (The Society of Dyers and Colourists, published), and known dyes described in Dyeing Notes (Color Dyeing Company). And oil soluble dyes, acid dyes, metal complex dyes, basic dyes, direct dyes, disperse dyes, mordant dyes and the like. Among these, oil-soluble dyes, acid dyes, metal complex dyes and basic dyes are preferable.
Further, according to the chemical structure, azo dyes, cyanine dyes other than cyanine dyes (ZC), triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, xanthene dyes, squaluliles dyes, And acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes.

<Binder resin>
The binder resin in the present invention disperses or penetrates a colorant, and examples thereof include thermoplastic resins and thermosetting resins. The resin is preferably a transparent resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light range. When used in the form of an alkali-developable photosensitive coloring composition, it is preferable to use an alkali-soluble vinyl-based resin obtained by copolymerizing an acidic substituent-containing ethylenically unsaturated monomer. Furthermore, in order to further improve the photosensitivity, an active energy ray curable resin having an ethylenically unsaturated double bond can also be used.

  As a thermoplastic resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin And polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin modified maleic resin, rosin modified fumaric resin, melamine resin, urea resin, and phenol resin.

  As a vinyl type alkali-soluble resin which copolymerized the acidic substituent containing ethylenic unsaturated monomer, resin which has acidic substituents, such as a carboxyl group and a sulfone group, is mentioned, for example. Specifically as the alkali-soluble resin, an acrylic resin having an acidic substituent, an α-olefin / (maleic anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, Or isobutylene / (anhydride) maleic acid copolymer and the like. Among them, at least one resin selected from an acrylic resin having an acidic substituent and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, is preferably used because it has high heat resistance and transparency. Be

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins in which an ethylenically unsaturated double bond is introduced by the method (i) or (ii) shown below.

[Method (i)]
As the method (i), for example, to a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers. And the carboxyl group of the unsaturated monobasic acid having an ethylenically unsaturated double bond is added, and the generated hydroxyl group is further reacted with a polybasic acid anhydride to form an ethylenically unsaturated double bond and a carboxyl group There is a way to introduce it.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate And 3,4-epoxycyclohexyl (meth) acrylates, which may be used alone or in combination of two or more. Glycidyl (meth) acrylate is preferred from the viewpoint of the reactivity with the unsaturated monobasic acid in the next step.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano-substituted, etc. Monocarboxylic acids and the like can be mentioned, and these may be used alone or in combination of two or more.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, which may be used alone or in combination of two or more. I do not mind. The remaining anhydride is obtained by using tricarboxylic acid anhydride such as trimellitic acid anhydride or using tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride, if necessary, such as increasing the number of carboxyl groups. It is also possible to hydrolyze the group, etc. In addition, when tetrahydrophthalic anhydride having an ethylenically unsaturated double bond, or maleic anhydride is used as a polybasic acid anhydride, the number of ethylenically unsaturated double bonds can be further increased.

  As an analogous method of the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of the carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As method (ii), using an ethylenically unsaturated monomer having a hydroxyl group, and copolymerizing the monomer of another unsaturated monobasic acid having a carboxyl group or another monomer There is a method of reacting the isocyanate group of the ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

  As the ethylenically unsaturated monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol There may be mentioned hydroxyalkyl methacrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, which may be used alone or in combination of two or more. In addition, polyether mono (meth) acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and / or butylene oxide etc. to the above hydroxyalkyl (meth) acrylate, poly γ-valerolactone, poly ε-caprolactone, and / or Polyester mono (meth) acrylates to which poly 12-hydroxystearic acid or the like is added can also be used. 2-hydroxyethyl methacrylate or glycerol methacrylate is preferable from the viewpoint of coating foreign matter suppression.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis [methacryloyloxy] ethyl isocyanate, but not limited thereto. Two or more types can be used in combination.

  In order to disperse the colorant preferably, the weight average molecular weight (Mw) of the resin is preferably in the range of 10,000 to 100,000, and more preferably in the range of 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  In addition, from the viewpoints of dispersibility, stability, developability, and heat resistance of the colorant, the colorant adsorbing group and the carboxyl group acting as an alkali-soluble group during development, and the fat acting as an affinity group to the colorant carrier and the organic solvent The balance of the aromatic group and the aromatic group is important for the dispersibility of the pigment, the developer permeability in the coating film, the developer solubility of the uncured portion, and the durability, and a resin with an acid value of 20 to 300 mg KOH / g It is preferable to use If the acid value is less than 20 mg KOH / g, the solubility in a developer is poor, and it is difficult to form a fine pattern. When it exceeds 300 mg KOH / g, fine patterns may not be left.

  The binder resin is preferably used in an amount of 30 parts by weight or more based on 100 parts by weight of the total weight of the colorant, because the film forming property and the various resistances are good. Is preferably used in an amount of 500 parts by weight or less. More preferably 100 to 400 parts by weight. More preferably, it is 160 to 320 parts by weight. The chromaticity region can be expanded by the composition ratio of such a colorant.

<Organic solvent (D)>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and infiltrated into the coloring agent carrier, and the filter segment is coated by applying a dry film thickness of 0.2 to 5 μm on a substrate such as a glass substrate. An organic solvent (D) is included to facilitate formation. The organic solvent (D) is selected in consideration of the solubility of each component of the coloring composition as well as the safety, as well as the coating properties of the coloring composition being good.
The organic solvent (D) can adjust the coloring composition to an appropriate viscosity and form a filter segment having an intended uniform film thickness, so an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the coloring agent It is preferred to use.

  The coloring composition for color filters of the present invention contains an organic solvent (D1) having a hydroxyl group as the organic solvent (D), and the organic solvent (D1) having a hydroxyl group is 100 weight in total of the organic solvent (D) 10% by weight or more in%. Thus, by containing the organic solvent (D1) having a specific amount of a hydroxyl group, the spectral characteristics of the coloring composition, heat resistance, coating properties of the coloring composition, and chemical resistance of the photosensitive coloring composition are improved. be able to.

(Organic solvent having a hydroxyl group (D1))
The organic solvent having a hydroxyl group (D1) is not limited as long as it is an organic solvent having one or more hydroxyl groups. By containing the organic solvent (D1) having a hydroxyl group, solvation occurs due to the hydrogen bond of the cyanine dye (ZC) and the organic solvent (D1), and the heat resistance of the dye is improved. Heat resistance is good.
The content of the organic solvent (D1) is 10% by weight or more in 100% by weight in total of the organic solvent (D), whereby the heat resistance of the dye becomes good, preferably 20 to 100% by weight. Preferably, it is 25 to 100% by weight.
By containing 10% by weight or more, the spectral characteristics become excellent.

As the organic solvent (D1) having a hydroxyl group, for example, an organic solvent having an ester group (solvent containing COO-), an organic solvent having an ether group other than an ester group (solvent containing -O-), esters other than esters It can be selected from organic solvents having a ketone group (solvents containing -CO-), alcohols other than the above, and the like.
Among these, an organic solvent having a ketone group or an ester group is preferable, and an organic solvent having an ester group is more preferable, because it can be particularly excellent in chemical resistance.

Further, as the organic solvent (D1) having a hydroxyl group, the solubility parameter (= SP value) is preferably 16 MPa ^1/2 or more and less than 24 MPa ^1/2 for the stability of the pigment dispersion, and more preferably, It is the range of 18 MPa ^1/2 or more and less than 23 MPa ^1/2 .

Although the following organic solvents are mentioned as a specific organic solvent (D1) (SP value MPa1 ^{/ 2} ), It is not limited to these.
Examples of the organic solvent having an ester group include methyl lactate (22.5), ethyl lactate (20.5), butyl lactate (18.4), methyl 2-hydroxyisobutanoate and the like.
Examples of the organic solvent having an ether group include methyl cellosolve (23.3), ethyl cellosolve (21.5), butyl cellosolve (19.4), ethylene glycol monopropyl ether (20.4), and diethylene glycol monomethyl ether. Ether (22.3), diethylene glycol monoethyl ether (21.9), diethylene glycol monobutyl ether (20.5), ethylene glycol monomethyl ether (24.8), ethylene glycol monoethyl ether (23.5), ethylene glycol mono Butyl ether (22.3), dipropylene glycol monomethyl ether (17.6), propylene glycol monomethyl ether (21.7), tripropylene glycol monomethyl ether (17.8), ethylene glycol Monoisopropyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol Monopropyl ether, propylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monopropyl ether and the like can be mentioned.

  As an organic solvent which has a ketone group, diacetone alcohol (18.8) etc. are mentioned, for example.

Examples of alcohols include methanol (29.7), ethanol (26.0), propanol (24.3), butanol (23.3), hexanol (21.9), cyclohexanol (23.3), Octanol (21.7), ethylene glycol (32.9), propylene glycol (20.7), glycerin (36.2), 1,3-butanediol (13.9), 2-methyl-1,3- Propanediol, 3-methyl-1,3-butanediol and the like can be mentioned.
These organic solvents can be used alone or in combination of two or more at an arbitrary ratio as needed.

That, among these organic solvents (D1), an organic solvent is preferred for chemical resistance with a ketone or ester groups, also the solubility parameter (= SP value) of 16 MPa ^1/2 or more 24MPa less than ^1/2 Is preferred for the stability of the pigment dispersion.

More preferably, an organic solvent having a ketone group or an ester group, and a solubility parameter (= SP value) of 16 MPa ^1/2 or more 24MPa less than ^1/2, particularly preferably 18 MPa ^1/2 or more 23MPa less than ^1/2 Chemical resistance and pigment dispersion stability by using methyl lactate (22.5), ethyl lactate (20.5), butyl lactate (18.4) and diacetone alcohol (18.8) It can be particularly excellent in sex.
Particularly preferred is ethyl lactate.

(Other organic solvents)
As the organic solvent (D), other organic solvents other than the hydroxyl group-containing organic solvent (D1) can be used in combination.
As other organic solvents, for example, 1,2,3-trichloropropane, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 3,5,5-trimethyl-2-cyclohexene-1 -One, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dibenzene Chlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p -Diethylbenzene, sec-butylbenzene, te t-Butylbenzene, γ-butyrolactone, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, triacetin, propylene glycol Cole diacetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, methyl isobutyl ketone, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic An acid ester etc. are mentioned.
These organic solvents can be used alone or in combination of two or more in any ratio as required.

  Among them, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc., because of good dispersibility of colorant, permeability and coatability of coloring composition. It is preferable to use ketones such as glycol acetates and cyclohexanone of the following.

<Photopolymerizable monomer>
The photopolymerizable monomer which may be added to the coloring composition of the present invention includes a monomer or an oligomer which is cured by ultraviolet light, heat or the like to form a transparent resin.

Examples of monomers and oligomers that cure by ultraviolet light and heat to form a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglyci Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Various acrylic and methacrylic esters such as (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxy ester Examples include, but not limited to, chill (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used alone or in combination of two or more at an arbitrary ratio as needed.

  The compounding amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability. .

<Photoinitiator>
A photopolymerization initiator is added to the coloring composition of the present invention to cure the composition by ultraviolet irradiation and to form a filter segment by photolithography, and a solvent development type or alkali development type photosensitive coloring composition It can be prepared in the form of

As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dil dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone, or 2,4-diethyl thioxanthone Thioxanthone compounds of the formula: 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphen) Nyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxy) Oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6) Phosphine compounds such as -trimethyl benzoyl) phenyl phosphine oxide or 2,4, 6 -trimethyl benzoyl diphenyl phosphine oxide; quinone compounds such as 9, 10- phenanthrene quinone, camphor quinone, ethyl anthraquinone; borate compounds; Carbazole compounds; imidazole compounds; or titanocene compounds are used.
These photopolymerization initiators can be used alone or in combination of two or more at an arbitrary ratio as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
As sensitizers, unsaturated ketones represented by chalcone derivatives, dibenzalacetone etc., 1,2-diketone derivatives represented by benzyl and camphorquinone etc., benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapyrazino porphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylo porphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrilium derivative, tetraphyrin derivative, anurene derivative, spiropyran derivative, spirooxazine Derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester, acyl phosphine oxide, methylphenyl glyoxylate, benzyl, 9, 10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, or 4,4′-tetra (t-butylperoxycarbonyl) benzopheno And 4,4'-diethylaminobenzophenone and the like.
These sensitizers can be used alone or in combination of two or more at an arbitrary ratio as required.

  More specifically, edited by Ogawara Shin et al., "Dye Handbook" (1986, Kodansha), edited by Ogawara Shin et al., "Chemicals of functional dyes" (1981, CMC), edited by Ikemori Tadajiro et al. Specific examples thereof include, but are not limited to, the sensitizers described in “Specially functional materials” (1986, CMC). In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the coloring composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Multifunctional thiol>
The photosensitive coloring composition of the present invention can contain a multifunctional thiol which acts as a chain transfer agent.
The polyfunctional thiol may be any compound having two or more thiol groups, and examples thereof include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bis thioglycolate, ethylene glycol bis thiopropionate, trimethylol propane tris thio glycolate, trimethylol propane tris thio propionate, trimethylol propane tris (3-mercaptobutyrate), pentaerythritol tetrakis thio glycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene,
2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. These polyfunctional thiols can be used alone or in combination of two or more at any ratio as required.

  The content of the multifunctional thiol is preferably 0.1 to 30% by weight, and more preferably 1 to 20% by weight based on the total solid content of the photosensitive coloring composition (100% by weight). When the content of the polyfunctional thiol is less than 0.1% by weight, the addition effect of the multifunctional thiol is insufficient, and when it exceeds 30% by weight, the sensitivity is too high and the resolution is lowered.

<Antioxidant>
The coloring composition for color filters of the present invention can also contain an antioxidant. In order to prevent the photopolymerization initiator and the thermosetting compound contained in the coloring composition for color filter from being oxidized and yellowed due to a heat process at the time of heat curing or ITO annealing, the antioxidant is the transmittance of the coating film. Can be raised. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation in the heating step and to obtain a high transmittance of the coating film.

  The "antioxidant" in the present invention may be a compound having an ultraviolet light absorbing function, a radical trapping function, or a peroxide decomposing function, and specifically, a hindered phenol type or hindered amine type as an antioxidant. Examples thereof include phosphorus, sulfur, benzotriazole, benzophenone, hydroxylamine, salicylate and triazine compounds, and known ultraviolet light absorbers, antioxidants and the like can be used.

  Among these antioxidants, preferred are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants or sulfur-based antioxidants from the viewpoint of achieving both the transmittance and sensitivity of the coating film. Agents. Also, more preferably, hindered phenol antioxidants, hindered amine antioxidants, or phosphorus antioxidants are used.

  Examples of hindered phenolic antioxidants include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di) -Tert-Butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-tert-butyl-4-4 Nonylphenol, 2,2'-Isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-Butylidene-bis- (2-t-butyl-5-methylphenol), 2,2'-thio- S- (6-t-Butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'-thiodiethyl bis- (3,5-di-t-butyl-4-hydroxyphenyl) ) -Propionate, 1,1,3-Tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydro) And the like. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.

  As the hindered amine antioxidant, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4) -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butane tetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-Tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-Pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomeric types having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  As a phosphorus antioxidant, tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 'isopropylidene diphenol alkyl phosphite, tris nonyl phenyl phosphite, tris dinonyl phenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-Di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidene bis (3-methyl-) 6-t-Butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxy phosphonyloxy)-Ben Zen, ethyl phosphite bis (2,4-di-tert-butyl-6-methylphenyl) and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As a sulfur-based antioxidant, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol, etc. may be mentioned. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, compounds of oligomer type and polymer type having a benzotriazole structure can be used.

  Specific examples of benzophenone-based antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2 -Hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2 And -hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  As a triazine type antioxidant, a 2, 4- bis (allyl) 6- (2-hydroxyphenyl) 1, 3, 5- triazine etc. are mentioned. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.

  Examples of the salicylate-based antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate and the like. In addition, oligomer type and polymer type compounds having a salicylate structure can also be used.

  These antioxidants can be used alone or in combination of two or more at an arbitrary ratio as required.

  The content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the coloring composition for color filter (100% by weight), since the lightness and sensitivity are good. .

<Amine compounds>
In addition, the coloring composition of the present invention can contain an amine compound having a function of reducing dissolved oxygen.

  As such an amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethyl paratoluidine etc. are mentioned.

<Leveling agent>
It is preferable to add a leveling agent to the colored composition of the present invention in order to improve the leveling properties of the composition on a transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie, and the like. As a specific example of dimethylsiloxane which has a polyester structure in a principal chain, BYK-310 by BYK-Chemie company, BYK-370, etc. are mentioned. The dimethylsiloxane having a polyether structure in the main chain and the dimethylsiloxane having a polyester structure in the main chain can also be used in combination. In general, the content of the leveling agent is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a low solubility in water while having a hydrophilic group, and when it is added to a coloring composition, It is characterized by low surface tension reduction ability, and in addition to low surface tension reduction ability, it is useful that the wettability to the glass plate is good, and the addition amount at which defects of the coating film due to foaming do not appear. Those which can sufficiently suppress the chargeability can be preferably used. As a leveling agent which has such a preferable characteristic, dimethylpolysiloxane which has a polyalkylene oxide unit can use it preferably. The polyalkylene oxide unit may be a polyethylene oxide unit or a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit to dimethylpolysiloxane is a pendent type in which the polyalkylene oxide unit is bonded to a repeating unit of dimethylpolysiloxane, a terminal-modified type bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane It may be any of linear block copolymer types alternately and repeatedly bonded. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2203. -2-207, but not limited thereto.

The leveling agent may be supplemented with an anionic, cationic, nonionic or amphoteric surfactant. The surfactant may be used as a mixture of two or more.
Examples of anionic surfactants to be added to leveling agents include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid Ester etc. are mentioned.

  Examples of the cationic surfactant added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. As a nonionic surfactant which is added to the leveling agent as auxiliaries, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And alkylbetaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines; and fluorine-based and silicone-based surfactants.

<Hardening agent, hardening accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening agent, the hardening accelerator, etc. as needed. As a curing agent, a phenolic resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound and the like are effective, but not particularly limited thereto, a thermosetting resin Any curing agent may be used as long as it can react with it. Among these, a compound having two or more phenolic hydroxyl groups in one molecule, and an amine curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg, dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg, Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Tyl-4-methylimidazole etc.), phosphorus compounds (eg triphenylphosphine etc.), guanamine compounds (eg melamine, guanamine, acetoguanamine, benzoguanamine etc.), S-triazine derivatives (eg 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6- Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct etc. can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin.

<Other additive components>
The coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity over time. Further, in order to enhance the adhesion to the transparent substrate, an adhesion improver such as a silane coupling agent may be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butyl pyrocatechol, tetraethyl phosphine, tetraphenyl phosphine, etc. Organic phosphine, phosphite and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the colorant.

  Adhesion improvers include vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinylsilanes such as vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3,3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyl trie Xysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the colorant in the coloring composition.

<Method of producing coloring composition>
The coloring composition of the present invention comprises a colorant, a colorant carrier such as a binder resin and / or an organic solvent, preferably together with a dispersion aid, a kneader, a 2-roll mill, a 3-roll mill, a ball mill, a horizontal sand mill It can be finely dispersed and manufactured using various dispersing means such as a vertical sand mill, an annular type bead mill, or an attritor (colorant dispersion). At this time, the cyanine dye (ZC), the organic pigment (B), the other colorant and the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. In addition, when the solubility of the colorant is high, specifically, the solubility in the organic solvent to be used is high, and if it is in a state where it is not dissolved by stirring and no foreign matter is observed, it is finely dispersed and manufactured as described above. There is no need.

  Moreover, when using as a photosensitive coloring composition for color filters (resist material), it can prepare as a solvent development type or an alkali development type coloring composition. The solvent-developable or alkali-developable coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, an organic solvent, another pigment dispersant, and an additive. It can be adjusted by mixing agents and the like. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

  The organic solvent (D1) may be added at the time of preparation for adding a photopolymerization initiator or the like to the colorant dispersion, even when used at the time of dissolution or dispersion of the cyanine dye (ZC). . Even when added at any stage, similar effects can be obtained with respect to optical characteristics, heat resistance and chemical resistance.

(Dispersion aid)
When the coloring agent is dispersed in the coloring agent carrier, it may contain a dispersing aid such as a dye derivative, a resin type dispersing agent and a surfactant as appropriate. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the coloring composition formed by dispersing the colorant in the colorant carrier using the dispersion aid has brightness and viscosity stability. It becomes good.

  Examples of dye derivatives include organic pigments, anthraquinones, acridones or triazines, compounds having a basic substituent, an acid substituent, or a phthalimidomethyl group which may have a substituent, for example, 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A 2001-335717, JP-A 2003- No. 128669, JP-A 2004-091497, JP-A 2007-156395, JP-A 2008-094873, JP-A 2008-094986, JP-A 2008-095007, JP-A 2008-195916 It is possible to use those described in Japanese Patent No. 4585581 etc. These may be used alone or in combination of two or more.

  The content of the dye derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more, with respect to 100 parts by weight of the colorant, from the viewpoint of improving the dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

  The resin type dispersant has a colorant affinity site having a property of adsorbing to the colorant, and a site compatible with the colorant carrier, and is adsorbed to the colorant to disperse the colorant in the colorant carrier Work to stabilize the Specific examples of the resin type dispersant include polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt , Polysiloxane, long chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) with polyester having free carboxyl group, and salts thereof Etc., (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Resin, water soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK. -P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen et al., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160, manufactured by Japan Lubrizol Corporation. 0, 17000, 18000, 20000, 21000, 21000, 24000, 26000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500 etc., BASF Company EFKA-46, 47, 48, 452, 4008, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554 1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; alkyl dimethylamino There may be mentioned amphoteric surfactants such as alkyl betaines such as betaine acetate and alkyl imidazolines, which may be used alone or in combination of two or more, but it is not necessarily limited thereto.

  When a resin type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, and more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the resin type dispersant and the surfactant is less than 0.1 parts by weight, the added effect is hardly obtained, and when the content is more than 55 parts by weight, the dispersing agent is influenced by the excess dispersant. May affect.

<Removal of coarse particles>
The coloring composition of the present invention may be coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, filtration with a sintered filter or membrane filter, and the like. It is preferable to carry out the removal of the mixed dust. Thus, the coloring composition preferably contains substantially no particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.

The color filter of the present invention comprises, on a substrate, a filter segment and / or a black matrix formed from the coloring composition for a color filter of the present invention, and a common color filter is, for example, a black matrix , Red, green and blue filter segments. The filter segment may further comprise a magenta filter segment, a cyan filter segment, and a yellow filter segment.
Among them, it is preferable to use the coloring composition for a color filter of the present invention for the formation of a red or blue filter segment, since a high effect is obtained due to color characteristics.
More preferably, it is a red filter segment.

  As the substrate, a glass substrate such as soda lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc., which is a transparent substrate, can be used. . In addition, on the surface of a glass plate or a resin plate, a transparent electrode made of indium oxide, tin oxide or the like may be formed for driving liquid crystal after panelization.

  If the black matrix is formed in advance before forming the filter segments on the substrate, the contrast of the liquid crystal display panel can be further enhanced. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed is used, but the invention is not limited thereto. A black matrix formed from is preferred. Alternatively, thin film transistors (TFTs) may be formed in advance on the transparent substrate or the reflective substrate, and then filter segments may be formed. By forming the filter segments and / or the black matrix on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

  The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When the coated film is dried, a vacuum dryer, a convection oven, an IR oven, a hot plate or the like may be used.

  The formation of each color filter segment and black matrix by the photolithographic method is carried out by the following method. That is, the coloring composition for color filter prepared as a coloring composition for solvent development type or alkali development type coloring color filter is dried on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It apply | coats so that a film thickness may be 0.2-10 micrometers. The film dried if necessary is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film.

  Thereafter, it is immersed in a solvent or an alkaline developer, or the developer is sprayed by a spray or the like to remove an uncured portion and form a desired pattern to form a filter segment and a black matrix. Furthermore, heating may be applied as needed to promote polymerization of the filter segment and black matrix formed by development. According to the photolithography method, filter segments and a black matrix can be formed with higher accuracy than the printing method.

In the development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a developing method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid buildup) developing method or the like can be applied.
In order to increase the ultraviolet exposure sensitivity, after applying and drying the color composition for color filter, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen. After film formation, UV exposure can also be performed.

  An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, etc. are formed on the color filter as needed.

  The color filter is bonded to the opposing substrate using a sealing agent, and liquid crystal is injected from the injection port provided in the seal portion, and then the injection port is sealed, and a polarizing film or retardation film is formed on the outside of the substrate as necessary. By bonding, a liquid crystal display panel is manufactured.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), critical alignment (VA), and optically convensend bend (OCB). Etc. can be used in a liquid crystal display mode in which coloring is performed using a color filter.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereby. In Examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

  First, the method of measuring the weight average molecular weight (Mw) of the resin will be described.

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin was measured using a TSK gel column (manufactured by Tosoh Corporation) and a GPC equipped with a RI detector (HLC-8120GPC manufactured by Tosoh Corporation), using polystyrene as the developing solvent and polystyrene conversion It is a weight average molecular weight (Mw).

  Subsequently, binder resins, cationic cyanine dyes, compounds having an imidate anion represented by the general formula (2), and compounds having a fluorine group-containing boron anion represented by the general formula (3) used in Examples and Comparative Examples , A compound having a methide acid anion represented by the general formula (4), a vinyl resin having a structural unit represented by the general formula (5), a cyanine dye solution, and a method for producing a finely divided pigment, and a resin type dispersant solution And a method of preparing a pigment dispersion and a green photosensitive coloring composition.

<Method of producing binder-resin solution>
(Acryl resin solution (R-1))
196 parts of propylene glycol monomethyl ether acetate is charged into a reaction vessel in which a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer are attached to a separable four-necked flask, the temperature is raised to 80 ° C, and the inside of the reaction vessel is purged with nitrogen. After the addition, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate ("Alonix M110" manufactured by Toagosei Co., Ltd.) from a dropping pipe A mixture of 20.7 parts and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, approximately 2 parts of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and propylene glycol monomethyl is obtained so that non-volatile content is 30% by weight in the previously synthesized resin solution. Ether acetate was added to prepare an acrylic resin solution (R-1). The weight average molecular weight (Mw) was 26000.

(Acryl resin solution (R-2))
After charging 196 parts of ethyl lactate in a reaction vessel in which a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer are attached to a separable four-necked flask, the temperature is raised to 80 ° C. and the inside of the reaction vessel is purged with nitrogen, From a dropping pipe, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate ("Alonix M110" manufactured by Toagosei Co., Ltd.) 20. A mixture of 7 parts and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, approximately 2 parts of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and ethyl lactate is added to the previously synthesized resin solution so that non-volatile content is 30% by weight. An acrylic resin solution (R-2) was prepared by addition. The weight average molecular weight (Mw) was 26000.

<Method of synthesizing cationic cyanine dye>
The following cationic cyanine dyes were synthesized with reference to J. Org. Chem., 1995, 60 (8), pp 2411-2422, J. Am. Chem. Soc., 2011, 133 (40), pp 15870-15873. .
The cationic cyanine dyes in the present invention were respectively synthesized according to the following reaction schemes 1 to 3.

(Cationic cyanine dye (A-1))
For the cationic cyanine dye (A-1), first, an intermediate (a-1) was synthesized, and then in the next step, the target cationic cyanine dye (A-1) was synthesized.

"Synthesis of Intermediate (a-1)"
In a 100 ml four-necked flask equipped with a thermometer, a dropping wax and a condenser, 5 parts of 2,3,3-trimethylindolen, 7.35 parts of iodoethane and 10 ml of acetonitrile were added, and the mixture was heated under reflux for 24 hours. After cooling to room temperature, the solvent was distilled off with an evaporator to precipitate a solid. Thereto, 40 ml of diethyl ether was added, washed and suction filtered. This gave 8.61 parts of product. The yield was 87%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 188.25 (molecular weight 188.14).

"Synthesis of cationic cyanine dye (A-1)"
Intermediate (a-1) 8.61 parts, 15 ml of acetic anhydride was added to a 100 ml four-necked flask equipped with a thermometer, a dropping wax, a condenser, and a nitrogen flow pipe, to which triethyl orthoformate was added using a dropping wax. 05 parts were dropped and heated to reflux. After 1 hour, the solution was cooled to room temperature to precipitate a solid. The precipitated solid was suctioned off and washed with 30 ml of ethyl acetate and 30 ml of deionized water. Heated in a hot air drier at 40 ° C. overnight to give 6.16 parts of product. The yield was 88%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 385.33 (molecular weight: 385.26).

(Cationic cyanine dye (A-2))
The compound was synthesized in the same manner as in the intermediate (a-1) except that the iodoethane in the intermediate (a-1) was changed to iodohexane, to obtain 9.79 parts of a product (intermediate (a-2)) . The yield was 84%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 244.35 (molecular weight 244.21). It synthesize | combined similarly to cationic cyanine dye (A-1) except having used intermediate (a-2), and obtained 6.92 parts of cationic cyanine dyes (A-2). The yield was 84%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 497.51 (molecular weight 497.39).

(Cationic cyanine dye (A-3))
For the cationic cyanine dye (A-3), first, an intermediate (a-3) was synthesized, and in the next step, the target cationic cyanine dye (A-3) was synthesized.

"Synthesis of Intermediate (a-3)"
In a 100 ml four-necked flask equipped with a thermometer, a dropping wax and a condenser, 5 parts of 2,3,3-trimethylindolenine, 9.85 parts of 2- (4-bromo-butoxymethyl) -oxirane, potassium iodide 5 After adding .21 parts and 10 ml of acetonitrile, the mixture was heated to reflux for 24 hours. After cooling to room temperature, the solvent was distilled off with an evaporator to precipitate a solid. Thereto, 40 ml of diethyl ether was added, washed and suction filtered. 5.87 parts of product (intermediate (a-3)) are obtained. The yield was 52%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with m / z = 288.31 (molecular weight 288.20).

"Synthesis of Cationic Cyanine Dye (A-3)"
It synthesize | combined similarly to cationic cyanine dye (A-1) except having used intermediate (a-3), and obtained 5.54 parts cationic cyanine dye (A-3). The yield was 58%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 585.49 (molecular weight 585.37).

(Cationic cyanine dye (A-4))
Synthesis similar to intermediate (a-3) except that 2- (4-bromo-butoxymethyl) -oxirane of intermediate (a-3) was changed to (4-bromo-butyl) -carbamic acid vinyl ester To obtain 7.93 parts of a product (intermediate (a-4)). The yield was 59%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 301.31 (molecular weight 301.19). It synthesize | combined similarly to cationic cyanine dye (A-1) except having used intermediate (a-4), and obtained 3.76 parts cationic cyanine dye (A-4). The yield was 55%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was the desired product with the cationic component m / z = 611.48 (molecular weight 611.36).

(Cationic cyanine dye (A-5))
In the cationic cyanine dye (A-5), after the intermediate (a-5a) is synthesized first, the intermediate (a-5b) is synthesized in the next step, and the target product is cationic in the next step. The cyanine dye (A-5) was synthesized.

"Synthesis of Intermediate (a-5a)"
Synthesized in the same manner as in intermediate (a-3), except that 2- (4-bromo-butoxymethyl) -oxirane in intermediate (a-3) was changed to 3-bromopropionic acid, and 5.87 parts of The product (intermediate (a-5a)) was obtained. The yield was 52%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It confirmed that it was a target object by m / z = 232.25 (molecular weight 232.13).

"Synthesis of Intermediate (a-5b)"
Thermometer, dropping wax, 100 ml 3-neck flask equipped with a condenser, 9.81 parts of intermediate (a-5a), 15 ml of dichloromethane, 0.40 parts of 4- (N, N dimethyl) aminopyridine, 2-hydroxy 2.55 parts of ethyl methacrylate and 3.44 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride were added, and the mixture was stirred at room temperature for 24 hours. Liquid separation operation was performed twice with 30 ml of ion exchange water, and then the organic layer was washed twice with 50 ml of saturated saline. Five parts of magnesium sulfate was added, and after stirring for 30 minutes, the magnesium sulfate was filtered and the solvent was distilled off. It was dried by heating in a vacuum dryer at 40 ° C. overnight to obtain 5.46 parts of a product (intermediate (a-5b)). The yield was 71%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 344.31 (molecular weight 344.19).

"Synthesis of cationic cyanine dye (A-5)"
It synthesize | combined similarly to cationic cyanine dye (A-1) except having used intermediate (a-5b). 5.54 parts of the product (A-5) are obtained. The yield was 58%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 824.38 (molecular weight 824.25).

(Cationic cyanine dye (A-6))
The same as intermediate (a-1) except that 2,3,3-trimethylindolenine in intermediate (a-1) is changed to 2,3,3-trimethyl-4,5-benzo-3H-indole To give 7.59 parts of a product (intermediate (a-6)). The yield was 87%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 238.28 (molecular weight: 238.16). It synthesize | combined similarly to cationic cyanine dye (A-1) except having used intermediate (a-6), and obtained 5.79 parts cationic cyanine dye (A-6). The yield was 91%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 485.42 (molecular weight 485.30).

(Cationic cyanine dye (A-7))
Synthesized in the same manner as in intermediate (a-1), except that 2,3,3-trimethylindolenine in intermediate (a-1) was changed to 5-bromo-2,3,3-trimethylindolenine, 7.53 parts of product (intermediate (a-7)) are obtained. The yield was 91%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 266.18 (molecular weight 266.05). It synthesize | combined similarly to cationic cyanine dye (A-1) except having used intermediate (a-7), and obtained 5.89 parts cationic cyanine dye (A-7). The yield was 92%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 541.20 (molecular weight 541.08).

(Cationic cyanine dye (A-8))
Intermediate (a-1) and intermediate (a-1) were obtained except that 2,3,3-trimethylindolenine in intermediate (a-1) was changed to 5-chloro-2,3,3-trimethylindolenine and iodoethane to iodobutane It synthesize | combined similarly and obtained the product (intermediate (a-8)) of 8.58 parts. The yield was 88%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 250.28 (molecular weight 250.14). It synthesize | combined similarly to cationic cyanine dye (A-1) except having used intermediate (a-8), and obtained 6.44 part cationic cyanine dye (A-8). The yield was 89%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 509.38 (molecular weight 509.25).

(Cationic cyanine dye (A-9))
The same as intermediate (a-1) except that 2,3,3-trimethylindolenine of intermediate (a-1) is changed to 2,3,3,5-tetramethylindolenine and iodoethane is changed to iodobutane It synthesize | combined and obtained 9.07 parts products (intermediate (a-9)). The yield was 88%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 230.31 (molecular weight: 230.19). It synthesize | combined similarly to cationic cyanine dye (A-1) except having used intermediate (a-9), and obtained 6.44 part cationic cyanine dye (A-9). The yield was 85%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 469.46 (molecular weight 469.36).

(Cationic cyanine dye (A-10))
Intermediate (a-1) and intermediate (a-1) were obtained except that 2,3,3-trimethylindolenine in intermediate (a-1) was changed to 5-methoxy-2,3,3-trimethylindolenine and iodoethane to iodobutane It synthesize | combined similarly and obtained 8.58 parts products (intermediate (a-10)). The yield was 87%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 246.32 (molecular weight 246.19). It synthesize | combined similarly to cationic cyanine dye (A-1) except having used intermediate (a-10), and obtained 6.36 parts cationic cyanine dye (A-10). The yield was 88%. The compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the desired product was obtained with the cationic component m / z = 501.46 (molecular weight 501.35).

<Compound Having Imidate Anion Represented by General Formula (2)>
(Imidate anion compound (G-1))
3.58 parts (1.1 equivalents) of trifluoromethanesulfonamide, 5.53 parts (2 equivalents) of potassium carbonate, and 60 ml of acetonitrile were added to a four-neck separable flask equipped with a thermometer, a stirrer, and a condenser. Thereafter, 3.53 parts of pentafluorobenzenesulfonyl chloride was added in portions, and the mixture was heated to reflux for 5 hours. After cooling to room temperature, 400 ml of acetonitrile was added and stirred well, and then the filtrate obtained by suction filtration was concentrated to obtain 7.30 parts of a product. It was confirmed by ¹ H, ¹³ C-NMR spectrum (solvent: deuterated chloroform) measurement that the obtained compound is the target compound (imidic acid anion compound (G-1)).

(Imidate anion compound (G-2))
An imidate anion compound (G-2) was obtained in the same manner as in the synthesis of the imidate anion compound (G-1) except that p-fluorobenzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

(Imidate anion compound (G-3))
An imidate anion compound (G-3) was obtained in the same manner as in the synthesis of the imidate anion compound (G-1) except that p-trifluoromethylbenzene sulfonyl chloride was used instead of pentafluorobenzene sulfonyl chloride. .

(Imidate anion compound (G-4))
An imidate anion compound (G-4) was obtained in the same manner as in the synthesis of the imidate anion compound (G-1) except that p-trifluoromethylbenzenesulfonamide was used in place of trifluoromethanesulfonamide.

<Compound Having a Fluorine-Containing Boron Anion Represented by General Formula (3)>
The fluorine group-containing boron anion compound was synthesized with reference to JP-A-2011-201803.

(Fluorine group-containing boron anion compound (FBA-1))
1.7 parts of magnesium and 26.1 parts of tetrahydrofuran are charged in a degassed nitrogen-replaced reaction vessel, and cooled to 18 ° C. with a water bath. 17.3 parts of bromopentafluorobenzene and 26.1 parts of tetrahydrofuran are charged in a dropping funnel and added dropwise so that the temperature in the system does not exceed 25 ° C. After completion of the dropwise addition, the reaction is continued at 45 ° C. for 2 hours, and then the reaction solution is cooled to 20 ° C. Thereafter, 3.0 parts of dichlorophenyl borane is dropped from the dropping funnel so that the system temperature does not exceed 25 ° C. After completion of the addition, the reaction is continued at 65 ° C. for 2 hours to complete the reaction.
This solution is added to 50 parts of saturated aqueous sodium hydrogen carbonate solution, the organic layer is separated, the aqueous layer is washed twice with 10 parts of ethyl acetate, and the ethyl acetate layer obtained here is separated into the organic layer previously separated. added. The organic layer is desolvated, and the residue is washed twice with hexane, and the residue is dried under reduced pressure to obtain sodium phenyltris (pentafluorophenyl) borate (fluorinated group-containing boron anion compound (FBA-1), which is the object. 10.4 parts, yield 90% (purity 98% or more). The product (FBA-1) was identified by ¹ H-NMR and ¹⁹ F-NMR. In addition, absorption of B-C bond was confirmed in the vicinity of 980 cm ^-1 by infrared absorption spectroscopy (KBr tablet method).

(Fluorine group-containing boron anion compound (FBA-2))
1.7 parts of magnesium and 26.1 parts of tetrahydrofuran are charged in a degassed nitrogen-replaced reaction vessel, and cooled to 18 ° C. with a water bath. 17.3 parts of bromopentafluorobenzene and 26.1 parts of tetrahydrofuran are charged in a dropping funnel and added dropwise so that the temperature in the system does not exceed 25 ° C. After completion of the dropwise addition, the reaction is continued at 45 ° C. for 2 hours, and then the reaction solution is cooled to 20 ° C. After that, 2.4 parts of boron trifluoride diethyl ether complex is dropped from the dropping funnel so that the system temperature does not exceed 25 ° C. After completion of the addition, the reaction is continued at 65 ° C. for 12 hours.
This solution is added to 50 parts of saturated aqueous sodium hydrogen carbonate solution, the organic layer is separated, the aqueous layer is washed twice with 10 parts of ethyl acetate, and the ethyl acetate layer obtained here is separated into the organic layer previously separated. added. The organic layer is desolvated, and the residue is washed twice with hexane, and the residue is dried under reduced pressure to obtain sodium tetrakis (pentafluorophenyl) borate (the fluorine-containing boron anion compound (FBA-2)) which is the object Was obtained in a yield of 40% (purity of 98% or more). The product (FBA-2) was identified by ¹⁹ F-NMR. In addition, absorption of B-C bond was confirmed in the vicinity of 980 cm ^-1 by infrared absorption spectroscopy (KBr tablet method).

<A compound having a methide acid anion represented by the general formula (4)>
The methide acid anion was synthesized with reference to JP2009-155206A.

(Methide acid anion compound (M-1))
A thermometer is attached to a three-necked flask containing a PTFE stirrer (15 mm, φ = 6 mm), and a 1.0 M methylmagnesium bromide-tetrahydrofuran solution (manufactured by Tokyo Chemical Industry Co., Ltd.) 215 under a nitrogen stream through calcium chloride. After 7 parts were added and ice cooling, 11 parts of trifluoromethanesulfonyl fluoride was added at an internal temperature of 15 ° C. or less. The mixture was heated and stirred to an internal temperature of 40 ° C., 5 parts of trifluoromethanesulfonyl fluoride was again added, and the mixture was stirred at room temperature for 24 hours. After adding 200 M of 0.3 M aqueous potassium chloride solution and stirring well, tetrahydrofuran was distilled off with an evaporator. The precipitate is filtered off by suction filtration, and the obtained filtrate is purified by recrystallization with water to give potassium tris (trifluoromethanesulfonyl) methide (methide acid anion compound (M-1)) in a yield of 8.2 parts. Obtained. It was confirmed by ¹⁹ F-NMR that it was the desired product.

<Vinyl-Based Resin Having Structural Unit Represented by General Formula (5)>
(Resin having an anionic group (AJ-1))
In a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 20.0 parts of 2-acrylamido-2-methylpropanesulfonic acid, 12.5 parts of methyl methacrylate, 20.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 3.0 parts of methacrylic acid, 2 -After 16.5 parts of hydroxyethyl methacrylate, 6.5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 25.1 parts of methyl ethyl ketone have been made uniform, they are charged into a dropping funnel, and 4 ports It was attached to a separable flask and dropped over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more, the weight average molecular weight (Mw) was 3390, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, a resin component (AJ-1) having an anionic group of 47% by weight was obtained.

(Resin having an anionic group (AJ-2 to 4))
Resin (AJ-2 to 4) was obtained in the same manner as resin (AJ-1) except that the composition and the compounding amount (parts by weight) shown in Table 1 were changed.

<Cyanine Dye (ZC) Represented by General Formula (1)>
(Cyanine dye (ZC-1))
A cyanine dye (ZC-1) comprising a cationic cyanine dye and a resin (AJ-1) having an anionic group was produced by the following procedure.

  A resin (AJ-1) having 57.1 parts of an anionic group and 1.5 parts of sodium hydroxide are added to 2000 parts of water, sufficiently mixed by stirring, and then heated to 60 ° C. On the other hand, an aqueous solution in which 10 parts of the cationic cyanine dye (A-1) is dissolved in 45 parts of water and 45 parts of methanol is prepared and dropped little by little into the above resin solution. After the dropwise addition, the mixture is stirred at 60 ° C. for 120 minutes to carry out a sufficient reaction. In order to confirm the end point of the reaction, the reaction solution was dropped on filter paper, and it was judged that a salt forming compound was obtained with the point where bleeding was eliminated as the end point. Thereafter, the solvent is removed by evaporation under reduced pressure using an evaporator and concentrated, and the concentrate is added dropwise to 1000 parts of water while stirring, and the resulting precipitate is removed by suction filtration, washed with water, and the remaining structure on filter paper. The salt compound was dried by a drier to obtain a cyanine dye (ZC-1) which is a salt forming compound of 32 parts of the cationic cyanine dye (A-1) and the resin (AJ-1) having an anionic group. . Salt, which is a by-product of salt exchange reaction of dye and resin, trace amount of unreacted dye, and unreacted resin can be removed at the time of suction filtration because they dissolve in water when the concentrate is dropped into water with stirring . Also, the by-products that remain slightly after the subsequent water washing are completely removed.

(Cyanine dyes (ZC-2 to 13, 21))
A cationic cyanine dye and an anionic group in the same manner as the cyanine dye (ZC-1) except that the type and blending amount (parts by weight) of the cationic cyanine dye and the resin having an anionic group shown in Table 2 are changed. Cyanine dyes (ZC-2 to 13, 21), which are salt forming compounds comprising a resin having As Basic.Red.12 (C.I. Basic Red 12) used for the cyanine dye (ZC-21), Aiden Astra Phloxine manufactured by Hodogaya Chemical Co., Ltd. was used.

(Cyanine dye (ZC-14))
The cyanine dye (ZC-14) which is a salt forming compound which consists of a cationic cyanine dye and an imide acid anion compound (G-1) was manufactured in the following procedure.

  Dissolve 9.69 parts of the imide acid anion (G-1) and 10 parts of the cationic cyanine dye (A-8) in a mixed solvent of 100 parts of water, 300 parts of methanol, 100 parts of methyl ethyl ketone and 100 parts of acetone The mixture was stirred at 60 ° C. for 240 minutes to sufficiently react. After that, the solvent was removed by evaporation under reduced pressure using an evaporator, and the solution was concentrated to take out a solid which is a salt forming compound. 1000 parts of water was added to this solid, and stirred at 25 ° C. for 180 minutes, followed by suction filtration to remove salts as a by-product. In addition, the salt-forming compound remaining on the filter paper was further washed by sprinkling with 400 parts of water to completely remove the by-product salt, and then the salt-forming compound was taken out. The salt forming compound taken out is dried by a drier, and 14.3 parts of a cyanine dye (ZC-) which is a salt forming compound of the cationic cyanine dye (A-8) and the imidic acid anion compound (G-1). 14) I got it.

(Cyanine dyes (ZC-15 to 17, 22, 24))
Various cationic cyanine dyes and various kinds of cationic cyanine dyes and various kinds of compounded amounts (parts by weight) of the cationic cyanine dye and the imide anion compound are changed to the contents shown in Table 2 in the same manner as the cyanine dye (ZC-14) A cyanine dye (ZC-15 to 17, 22, 24) which is a salt forming compound comprising an imide acid anion compound was produced. As Basic.Red.12 (C.I. Basic Red 12) used for the cyanine dye (ZC-22), Aiden Astra Phloxine manufactured by Hodogaya Chemical Co., Ltd. was used.

(Cyanine dye (ZC-18))
A cyanine dye (ZC-18), which is a salt forming compound composed of a cationic cyanine dye and a fluorine group-containing boron anion compound (FBA-1), was produced by the following procedure.

  Dissolve the cationic cyanine dye (A-8) in 10 parts of a mixed solvent of 300 parts of methanol, 100 parts of methyl ethyl ketone and 100 parts of acetone, and 12.79 parts of a fluorine group-containing boron anion compound (FBA-1) in 1000 parts of water in advance ) Is mixed dropwise. Then, it stirred at 60 degreeC for 240 minutes, and reacted fully. After that, the solvent was removed by evaporation under reduced pressure using an evaporator, and the solution was concentrated to take out a solid which is a salt forming compound. 1000 parts of water was added to this solid, and stirred at 25 ° C. for 180 minutes, followed by suction filtration to remove salts as a by-product. In addition, the salt-forming compound remaining on the filter paper was further washed by sprinkling with 400 parts of water to completely remove the by-product salt, and then the salt-forming compound was taken out. The salt forming compound taken out is dried by a drier, and a cyanine dye (ZC) which is a salt forming compound of 14.3 parts of a cationic cyanine dye (A-8) and a fluorine group-containing boron anion compound (FBA-1). -18) was obtained.

(Cyanine dyes (ZC-19, 23, 25))
Various cationic cyanines in the same manner as the salt forming compound (ZC-18) except that the types and the blending amounts (parts by weight) of the cationic cyanine dye and the fluorine group-containing boron anion compound are changed to the contents shown in Table 2. The cyanine dye (ZC-19, 23, 25) which is a salt-forming compound of a dye and various fluorine-containing boron anion compounds was manufactured. As Basic.Red.12 (C.I. Basic Red 12) used for the cyanine dye (ZC-23), Aiden Astra Phloxine manufactured by Hodogaya Chemical Co., Ltd. was used.

(Cyanine dye (ZC-20))
The cyanine dye (ZC-20) which is a salt forming compound which consists of a cationic cyanine dye and a methide acid anion compound (M-1) was manufactured in the following procedure.

  Dissolve 9.94 parts of the methide acid anion compound (M-1) and 10 parts of the cationic cyanine dye (A-8) in a mixed solvent of 100 parts of water, 300 parts of methanol, 100 parts of methyl ethyl ketone and 100 parts of acetone And stirred at 60.degree. C. for 240 minutes to sufficiently react. After that, the solvent was removed by evaporation under reduced pressure using an evaporator, and the solution was concentrated to take out a solid which is a salt forming compound. 1000 parts of water was added to this solid, and stirred at 25 ° C. for 180 minutes, followed by suction filtration to remove salts as a by-product. In addition, the salt-forming compound remaining on the filter paper was further washed by sprinkling with 400 parts of water to completely remove the by-product salt, and then the salt-forming compound was taken out. The salt forming compound taken out is dried by a drier, and 12.1 parts of a cyanine dye (ZC-) which is a salt forming compound of the cationic cyanine dye (A-8) and the methide acid anion compound (M-1). 20).

(Cyanine dye (ZC-26))
The cyanine dye (ZC-26) which is a salt forming compound which consists of a cationic cyanine dye and sodium tetrafluoroboron was manufactured in the following procedure.

  A cationic cyanine dye (A-1) was dissolved in 300 parts of methanol, 100 parts of methyl ethyl ketone and 100 parts of acetone in 10 parts of a mixed solvent, and 2.5 parts of sodium tetrafluoroborohydride was dissolved in 1000 parts of water in advance. The solution is mixed dropwise. Then, it stirred at 60 degreeC for 240 minutes, and reacted fully. After that, the solvent was removed by evaporation under reduced pressure using an evaporator, and the solution was concentrated to take out a solid which is a salt forming compound. 1000 parts of water was added to this solid, and stirred at 25 ° C. for 180 minutes, followed by suction filtration to remove salts as a by-product. In addition, the salt-forming compound remaining on the filter paper was further washed by sprinkling with 400 parts of water to completely remove the by-product salt, and then the salt-forming compound was taken out. The salt-formed compound taken out was dried by a drier to obtain 14.3 parts of a cyanine dye (ZC-26) which is a salt-formed compound consisting of a cationic cyanine dye (A-1) and sodium tetrafluoroboron. .

(Cyanine dye (ZC-27))
The cyanine dye (ZC-27) which is a salt forming compound which consists of a cationic cyanine dye and sodium perchlorate was manufactured in the following procedures.

  A cationic cyanine dye (A-1) was dissolved in 300 parts of methanol, 100 parts of methyl ethyl ketone and 100 parts of acetone in 10 parts of a mixed solvent, and 2.5 parts of sodium perchlorate was dissolved in 1000 parts of water in advance. The solution is mixed dropwise. Then, it stirred at 60 degreeC for 240 minutes, and reacted fully. After that, the solvent was removed by evaporation under reduced pressure using an evaporator, and the solution was concentrated to take out a solid which is a salt forming compound. 1000 parts of water was added to this solid, and stirred at 25 ° C. for 180 minutes, followed by suction filtration to remove salts as a by-product. In addition, the salt-forming compound remaining on the filter paper was further washed by sprinkling with 400 parts of water to completely remove the by-product salt, and then the salt-forming compound was taken out. The salt forming compound taken out was dried by a drier to obtain 14.3 parts of a cyanine dye (ZC-27), which is a salt forming compound consisting of a cationic cyanine dye (A-1) and sodium perchlorate. .

<Method for producing cyanine dye solution>
(Cyanine dye solution (SY-1))
The following mixture was subjected to ultrasonic irradiation for 1 hour to obtain a cyanine dye solution (SY-1).

Cyanine dye (ZC-1): 6.0 parts Acrylic resin solution (R-1): 30.0 parts Cyclohexanone: 14.0 parts

(Cyanine dye solution (SY-2 to 27))
By the same method as the cyanine dye solution (SY-1) except that the cyanine dye (ZC-1) and the organic solvent D in the preparation of the cyanine dye solution (SY-1) were changed to the compositions described in Table 3 Cyanine dye solution and xanthene dye solution (SY-2 to 27) were obtained.

<Method of producing finely divided pigment>
(Fined yellow pigment (PY139-1))
Yellow pigment C.I. I. Pigment Yellow 139 ("PARIOTOL ERO D 1819" manufactured by BASF Corporation), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , And a finely divided yellow pigment (PY139-1) was obtained.

(Fined yellow pigment (PY150-1))
Yellow pigment C.I. I. Pigment Yellow 150 (Lanexcess "E-4GN"), 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 80 ° C for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. And finely divided yellow pigment (PY150-1) were obtained.

(Fined red pigment (PR254-1))
Red pigment C.I. I. 200 parts of CI pigment red 254 ("B-CF" manufactured by BASF Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 80C for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , A finely divided red pigment (PR254-1) was obtained.

(Fined red pigment (PR177-1))
Red pigment C.I. I. Pigment Red 177 ("Chromophthal Red A2B" manufactured by BASF Corporation), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 80 ° C for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , A finely divided red pigment (PR177-1) was obtained.

(Fined red pigment (PR166-1))
Red pigment C.I. I. Pigment Red 166 ("CHROMOPHTAL SCARLET D 3540" manufactured by BASF Corporation), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 80 ° C for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , A finely divided red pigment (PR166-1) was obtained.

(Fined red pigment (PR224-1))
Red pigment C.I. I. Pigment Red 224 ("Perylene Red 224 R6420" manufactured by Sun Chemical Co., Ltd.), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 80 ° C for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , A finely divided red pigment (PR224-1) was obtained.

(Fined green pigment (PG 58-1))
Phthalocyanine-based green pigment C.I. I. Pigment green 58 ("FASTOGEN GREEN A110" manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 80 ° C for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. And a phthalocyanine-based finely divided green pigment (PG 58-1) was obtained.

(Fined blue pigment (PB 15: 6-1))
Phthalocyanine blue pigment C.I. I. Pigment blue 15: 6 ("LIONOL BLUE ES" manufactured by Toyo Color Co., Ltd., specific surface area 60 m2 / g) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts in a stainless steel 1 gallon kneader (Inoue Seisakusho), 80 ° C The mixture was kneaded for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. And a phthalocyanine-based finely divided blue pigment (PB 15: 6-1) was obtained.

<Preparation of Resin Type Dispersant Solution>
(Resin type dispersant solution 1)
A resin-type dispersant solution 1 was prepared by using a commercially available resin-type dispersant, EFKA 4300 manufactured by BASF, and propylene glycol monomethyl ether acetate to prepare a 40% by weight nonvolatile matter solution.

<Method of producing pigment dispersion>
(Pigment dispersion (P-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm The mixture was filtered through a filter of the following to make a pigment dispersion (P-1) having a non-volatile component of 20% by weight.

Refined yellow pigment (PR 139-1): 11.0 parts Acrylic resin solution (R-1): 23.3 parts Propylene glycol monomethyl ether acetate: 60.7 parts Resin type dispersant solution 1: 5.0 parts

(Pigment dispersion (P-2 to 8))
The same as pigment dispersion (P-1), except that the type of the finely divided organic pigment (fined yellow pigment (PR139-1)) in the production of pigment dispersion (P-1) is changed as shown in Table 4. Pigment dispersions (P-2 to 8) were prepared by the method of

<Method of producing green photosensitive coloring composition>
(Green photosensitive coloring composition (RG-1))
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a green photosensitive coloring composition (RG-1).

Pigment dispersion (P-7): 32.0 parts C.I. I. Pigment green 58
Pigment dispersion (P-2): 18.0 parts C.I. I. Pigment yellow 150
Acrylic resin solution (R-1): 7.5 parts photopolymerizable monomer ("Alonics M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts dipentaerythritol penta / hexaacrylate photopolymerization initiator (BASF AG) Manufactured by "OXE-02"): 1.5 parts of ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)
-9H-Carbazol-3-yl]-, 1- (O-acetyloxime)
Propylene glycol monomethyl ether acetate: 39.0 parts

Example 1
(Coloring composition (DP-1))
The following mixture was subjected to ultrasonic wave irradiation for 1 hour to obtain a colored composition (DP-1).

Cyanine dye (ZC-8): 12.0 parts Acrylic resin solution (R-2): 60.0 parts Organic solvent (D1); Ethyl lactate: 28.0 parts

Example 2
(Coloring composition (DP-2))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a colored composition (DP-2).

Cyanine dye solution (SY-1): 90.0 parts Organic solvent (D1); methanol: 10.0 parts

[Examples 3 to 38, Comparative Examples 1 to 4]
(Coloring composition (DP-3 to 42))
A coloring composition (coloring composition (DP-2) in the same manner as the coloring composition (DP-2) except that the pigment solution, the pigment dispersion, and the organic solvent (D) are changed to the types and blending amounts (parts by weight) shown in Table 5, respectively. DP-3 to 42) were obtained.

Description of abbreviations and SP values (MPa ^1/2 ) of the organic solvents used are described below.
(Organic solvent (D1)
Methanol (29.7)
Ethanol (26.0)
Hexanol (21.9)
Octanol (21.7)
PGME; propylene glycol monomethyl ether (21.7)
Diacetone alcohol (18.8)
Methyl lactate (22.5)
Ethyl lactate (20.6)
Butyl lactate (18.4)
Methyl cell solve (23.3)
Ethyl cell solve (21.5)
Butyl Cell Solve (19.4)

(Other organic solvents)
PGMAc; propylene glycol monomethyl ether acetate

<Evaluation of coloring composition>
The spectral properties, chemical resistance, and dispersion stability of the produced coating composition were evaluated for the obtained colored composition by the following method. Table 6 shows the evaluation results.

(Spectroscopic characterization)
The resulting colored composition is coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate by a spin coater so that x = 0.640, then dried at 70 ° C. for 20 minutes, and then 230 ° C. The coated substrate was produced by heating and cooling for 20 minutes. It baked at 230 degreeC in oven for 20 minutes, and the lightness (spectral transmission factor) was measured using the obtained application | coating board | substrate.
The measurement of the lightness (spectral transmittance) in the XYZ color system chromaticity diagram was performed using a spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.).
The judgment criteria are as follows. ◎ is a very good level, ○ is a good level, Δ ○ is a somewhat good level, Δ is a practical level, and × is a level not suitable for practical use.

: 1: 18.0 or more ○: 17.6 or more and less than 18.0 Δ ○: 17.2 or more and less than 17.6 Δ: 16.8 or more and less than 17.2 ×: less than 16.8

(Evaluation of chemical resistance of coating film)
The resulting photosensitive composition is coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, then heated at 230 ° C. for 20 minutes, allowed to cool By doing this, a coated substrate was produced. The coated substrate thus prepared was measured using a spectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.) after heat treatment at 230 ° C. to obtain x = 0.640. The chromaticity ([L * (1), a * (1), b * (1)) at the C light source of the coating film is measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) After that, it was immersed in NMP for 30 minutes as a chemical resistance test, and the chromaticity ([L * (2), a * (2), b * (2)) at C light source was measured, and the following calculation was made] The color difference ΔEab * is determined by the equation and evaluated in the following three steps: ○: good level, Δ: practical level, x: unpractical level.

ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )

○: ΔEab * is less than 1.5 Δ: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more

(Aging viscosity increase rate)
The colored composition is stored as an initial product for one day at 5 ° C. after preparation, and as an elapsed product after standing for 1 week at 40 ° C. The viscosity was measured at 25 ° C. and 20 rpm using Among the obtained results, the viscosity of the initial product was taken as the initial viscosity, and the viscosity of the product with time was taken as the viscosity over time.
The measured initial viscosity and the temporal viscosity were applied to the following equation to measure the temporal viscosity increase rate.
[Temporal viscosity increase rate] = (temporal viscosity / initial viscosity) × 100 (%)
The evaluation results were judged as follows.

:: 97.5% to 102.5% ○: 95.0% to 97.5% or 102.5% to 105.0% Δ: 90.0% to 95.0% or 105. 0% or more and less than 110.0% ×: less than 90.0% or 110.0% or more

From Table 6, the coloring composition containing the cyanine dye (ZC) of the present invention and the specific amount of the organic solvent (D1) was excellent in the spectral characteristics, and the chemical resistance and the temporal viscosity were also good. In the present specification, Examples 2 to 5 , 13 , 14 to 18, 23 , 25 , 27 to 32, 36 and 37 are reference examples.

[Example 39]
(Preparation of photosensitive coloring composition (RR-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a photosensitive coloring composition (RR-1).

Colored composition (DP-2): 12.5 parts acrylic resin solution (R-1): 24.6 parts Photopolymerization initiator: 1.1 parts oxime ester photopolymerization initiator (C1)
Ethan-1-one, 1- [9-ethyl-6- (2-methylbenzoyl)
-9H-Carbazol-3-yl], 1- (O-acetyloxime)
("IRGACURE OXE 02" manufactured by BASF Corporation)
Photopolymerizable monomer: 5.4 parts dipentaerythritol hexaacrylate ("Alonics M-402" manufactured by Toagosei Co., Ltd.)
Organic solvent (D): 56.4 parts Organic solvent (D1); Ethyl lactate

[Examples 39 to 45, Comparative Examples 5 to 8]
(Photosensitive coloring composition (RR-2 to 10))
A coloring composition in the same manner as the coloring composition (RR-1) except that the coloring composition, the acrylic resin solution, and the organic solvent (D) are changed to the types and blending amounts (parts by weight) shown in Table 7 respectively. (RR-2 to 11) were obtained. Ethyl lactate was used as the organic solvent (D1).

<Evaluation of photosensitive coloring composition>
Evaluation of the spectral characteristics and chemical resistance of the produced coating film was performed by the following method using the obtained photosensitive coloring composition. Table 8 shows the evaluation results.

(Spectroscopic characterization)
The obtained photosensitive coloring composition is coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate by a spin coater so as to be x = 0.640, and irradiated with ultraviolet light at an exposure amount of 50 mJ / cm ^2. After exposure, the film was spray developed for 30 seconds in a 0.2% by weight aqueous solution of sodium carbonate at 23 ° C., and baked at 230 ° C. for 20 minutes in an oven to obtain a coated substrate of the photosensitive coloring composition obtained. The lightness (spectral transmittance) was measured using the obtained coated substrate.
The measurement of lightness (spectral transmittance) in the XYZ color system chromaticity diagram was performed using a spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.) ◎: very good level, ○ Is a good level, .DELTA..smallcircle. Is a somewhat good level, .DELTA. Is a practical level, and x is a level not suitable for practical use.

: 1: 18.0 or more ○: 17.6 or more and less than 18.0 Δ ○: 17.2 or more and less than 17.6 Δ: 16.8 or more and less than 17.2 ×: less than 16.8

(Evaluation of chemical resistance of coating film)
The obtained photosensitive composition is coated on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and integrated light quantity using an ultra-high pressure mercury lamp Ultraviolet exposure was performed at 150 mJ / cm ² , and development was performed with an alkaline developer at 23 ° C. Next, the coated substrate was produced by heating at 230 ° C. for 20 minutes and leaving to cool. The coated substrate thus prepared was measured using a spectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.) after heat treatment at 230 ° C. to obtain x = 0.640. The chromaticity ([L * (1), a * (1), b * (1)) at the C light source of the coating film is measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) After that, it was immersed in NMP for 30 minutes as a chemical resistance test, and the chromaticity ([L * (2), a * (2), b * (2)) at C light source was measured, and the following calculation was made] The color difference ΔEab * is determined by the equation and evaluated in the following three steps: ○: good level, Δ: practical level, x: unpractical level.

ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )

○: ΔEab * is less than 1.5 Δ: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more and 5.0 or more

  From Table 8, the coloring composition containing the cyanine dye (ZC) of the present invention and the specific amount of the organic solvent (D1) was excellent in spectral characteristics, and was also excellent in heat resistance.

  Among them, the photosensitive coloring composition containing ethyl lactate as the organic solvent (D1) was particularly excellent in spectral characteristics.

<Method of producing blue photosensitive coloring composition>
(Blue photosensitive coloring composition (RB-1))
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a blue photosensitive colored composition (RB-1).

Pigment dispersion (P-7): 45.0 parts C.I. I. Pigment blue 15: 6
Cyanine dye solution (SY-1): 18.6 parts Acrylic resin solution (R-2): 2.5 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd. "ALONIX M-402"): 2.0 parts Pentaerythritol penta / hexaacrylate photoinitiator ("OXE-02" manufactured by BASF AG): 1.5 parts Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)
-9H-Carbazol-3-yl]-, 1- (O-acetyloxime)
Organic solvent (D1); Ethyl lactate: 30.4 parts

<Evaluation of blue photosensitive coloring composition>
(Coating film preparation and evaluation)
The same evaluation as that of the red photosensitive coloring composition is performed except that the coated substrate is obtained using the obtained blue photosensitive coloring composition so that x = 0.139 and y = 0.095 in a C light source. The
As a result, as in the case of the red photosensitive coloring composition, the result was excellent in fastness such as heat resistance and chemical resistance while having high brightness.

(Preparation of color filter)
A black matrix was patterned on a glass substrate, and a red coloring composition (RR-1) was applied on the substrate with a spin coater to form a colored film. The film was irradiated with ultraviolet light of 50 mJ / cm ² through a photomask using an extra-high pressure mercury lamp. Next, after spray development with an alkaline developer consisting of a 0.2% by weight aqueous solution of sodium carbonate to remove an unexposed portion, the substrate is washed with ion exchanged water and heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. Here, after the heat treatment at 230 ° C., the red filter segment was made to conform to a chromaticity of x = 0.655 and y = 0.325 (hereinafter also used for green and blue) in a C light source. Also, in the same manner, the green filter segment is made to match the chromaticity of x = 0.290, y = 0.600 using the green coloring composition (RG-1), and the blue filter segment is colored blue. The composition (RB-1) was used to match the chromaticity of x = 0.139 and y = 0.095, and each filter segment was formed to obtain a color filter.

  The coloring composition for color filters of the present invention has higher stability than the conventional ones and high lightness because of excellent spectral characteristics, and it has been confirmed that high-quality color filters can be obtained.

Claims (4)

It is a coloring composition for color filters containing a coloring agent, binder resin, and an organic solvent (D), and the coloring agent contains a cyanine dye (ZC) represented by the following general formula (1), and the organic The solvent (D) contains an organic solvent (D1) having a ketone group or ester group and a hydroxyl group, and the solubility parameter (SP value) of the organic solvent (D1) is 16 MPa ^1/2 or more and less than 24 MPa ^1/2 A coloring composition for a color filter, wherein the content of the organic solvent (D1) having hydroxyl groups is 10% by weight or more in 100% by weight of the total of the organic solvent (D).
[In the general formula (1),
A represents a carbon atom having a substituent or a hydrogen atom, or a sulfur atom.
R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, a substituted or no substituent It represents a substituted aryl group or a substituted or unsubstituted acyl group.
R ¹¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a halogen atom.
R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
Y ^- is a vinyl resin having a structural unit represented by the fluorine-containing boron anion represented by the following following general formula (3), methide anion represented by the following general formula (4), and the following general formula (5) And at least one selected from the group consisting of ]
[In the general formula (3),
R ^{31 to} R ³⁴ each independently represent an alkyl group which may be substituted by a fluorine atom, a cyano group, a hydrogen atom, a fluorine atom or an aryl group which may be substituted by a fluorine atom,
At least one of R ^{31 to} R ^{34 represents} an alkyl group which may be substituted with a fluorine atom, a fluorine atom, or an aryl group which may be substituted with a fluorine atom.
However, the case where all of R ^{31 to} R ³⁴ are fluorine atoms is excluded. ]
[In the general formula (4),
Each of R ^{41 to} R ⁴³ independently represents an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. ]
[In the general formula (5),
R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
Q represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, -CONH-R ^52- , or -COO-R ^52- ,
R ⁵² represents a substituted or unsubstituted alkylene group.
P ^- is, -SO ₃ ^-, or -COO ^- represents a. ]   The coloring composition for color filters according to claim 1, wherein the organic solvent (D1) is ethyl lactate.   The coloring composition for color filters according to claim 1 or 2, further comprising a photopolymerization initiator.   A color filter comprising a filter segment formed of the coloring composition for color filter according to any one of claims 1 to 3 on a substrate.