JP4867377B2 - Coloring composition, inkjet recording liquid, inkjet recording method, and color toner - Google Patents

Description

  The present invention relates to a color toner, a color filter, a coloring composition, an ink jet recording liquid, an ink jet recording method, and a metal chelate dye.

  Conventionally, as a method for obtaining a color hard copy, a color image recording technique has been studied by thermal transfer, ink jet, electrophotography, silver halide photosensitive material and the like. In addition, color filters are used in electronic parts such as LCDs and PDPs in displays and CCDs in photography equipment.

  The ink jet recording method is a recording method in which characters and images are obtained by ejecting and adhering ink droplets directly from a very fine nozzle to a recording member. This method has not only the advantage that the device used is low noise and good operability, but also the advantage that it can be easily colored and plain paper can be used as a recording member. ing.

  Ink-jet inks must be compatible with the recording method used, have high recording image density and good hue, excellent color image fastness such as light resistance, heat resistance and water resistance, It requires fast fixing on a medium, no bleeding after recording, excellent storability as ink, no safety problems such as toxicity and flammability, and low cost.

  From this point of view, various ink jet recording liquids have been proposed and studied, but there are very few recording liquids that satisfy many of the requirements at the same time.

  In color image recording using yellow, magenta, cyan, and black, for example, C.I. I. The conventionally known C.I. described in the index. I. Numbered dyes and pigments have been widely studied. For example, in magenta ink using a water-soluble dye, C.I. I. Although those using anthraquinone-based water-soluble dyes such as Direct Red 82 are known, they are difficult to increase the printing density and still have problems in fastness such as light resistance.

  Further, as a method for improving the light resistance of a dye, a method of coordinating a metal to a dye is generally known, and this method can be used for the production of an ink jet dye, and the dye and the metal can be contained in the same ink. It has been proposed (see, for example, Patent Document 1). However, this method has a drawback in the so-called storage stability of the ink, in which the dye is precipitated and clogging may occur at the nozzle of the ink jet because the solubility in water decreases by coordinating the metal to the dye. there were.

  Furthermore, an ink jet recording recording liquid containing an aqueous dispersion of polymer particles containing a dye coordinated with a metal has been proposed (see, for example, Patent Documents 2 to 4). There was a drawback in terms.

  As described above, it is difficult to satisfy all the performance items such as hue, fastness, and ink storage stability required for the ink-jet ink with the well-known dyes and pigments.

  In order to solve this problem, for magenta inks, methine dyes, azo dyes and water-based ink compositions thereof for the purpose of achieving both hue and light resistance are disclosed (for example, see Patent Document 5). The level of hue and light resistance is not sufficient, and further improvements have been desired.

  In the case of using a colorant for a color toner, in a color copier or color laser printer using an electrophotographic method, a colorant is generally adhered to a toner in which a colorant is dispersed in resin particles or a resin particle surface. Toner is used. Since the method of attaching a coloring material to the resin surface is coloring only the surface, it is difficult to obtain a sufficient coloring effect. Further, there are problems that the charging performance changes due to separation from the surface of the colorant, and the surface of the fixing roller is contaminated. Therefore, a toner in which a coloring material is dispersed inside a particle is widely used. The performance required for such a color toner includes color reproducibility, image transparency in an Over Head Projector (hereinafter referred to as OHP), and light resistance. Toners in which pigments are dispersed in particles as a coloring material have been disclosed (for example, see Patent Documents 6 to 8). However, these toners are excellent in light resistance, but are insoluble and thus easily aggregate and are transparent. The decrease in color and the hue change of the transmitted color are problems. On the other hand, a toner using a dye as a coloring material has been disclosed (see, for example, Patent Documents 9 to 13), and although improvements have been seen in terms of transparency and hue, it is still inadequate, and light fastness is less than that of a pigment. There was a problem that it deteriorated significantly compared with the case of using.

Since the color filter needs to have high transparency, a method called a dyeing method for coloring with a dye has been performed. For example, a photosensitive material to be dyed is applied to a substrate such as glass, followed by pattern exposure of one filter color, and washing the unexposed part in a development process to remove the remaining pattern part with the dye of the filter color. A color filter can be manufactured by sequentially repeating the operation such as dyeing for all the filter colors (see, for example, Patent Document 14). This method uses dyes and has high transmittance and excellent optical characteristics of the color filter, but there is a limit to light resistance, heat resistance, etc., and a color material with excellent resistance and high transparency is desired. It was. Therefore, organic pigments having excellent light resistance and heat resistance have been used instead of dyes, but it has been difficult to obtain excellent optical properties such as dyes with color filters using pigments.
JP-A-8-156399 JP 2001-18880 A JP 2001-26731 A JP 2002-121442 A (paragraph number 0029) Japanese Patent Laid-Open No. 10-72560 JP 62-157051 A Japanese Patent Laid-Open No. Sho 62-255556 JP-A-6-118715 JP-A-3-276161 JP-A-2-207274 JP-A-2-207273 Japanese Patent Laid-Open No. 10-20559 Japanese Patent No. 3513792 (Example) Japanese Patent Laid-Open No. 5-80213

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel metal chelate dye and a novel coloring composition containing the metal chelate dye, and an ink jet containing the novel metal chelate dye. The object is to provide a recording liquid, an ink jet recording method, a color toner, and a color filter.

1. A dye represented by the following formula (I), and characterized in that it contains at least one of the following general formula (V) with a compound metal chelate dye that will be formed from a metal ion-containing compound comprising a metal ion represented Coloring composition .

（式中、Ｒ_１２は置換基を表す。Ｒ_１３は炭素数２以上のアルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基、又はヘテロ環基を表す。Ｒ_１６は水素原子、メチル基、プロピル基、ブチル基、ペンチル基、オクチル基、ピバロイルアミノ基、シアノ基又はクロル基を表す。ｌは１から５の整数を表し、ｌが複数の場合、各々のＲ_１６は同一でも、異なっていても良い。ＸはＯ、Ｓ、ＳＯまたはＳＯ_２を表す。
２．前記一般式（Ｉ）が下記一般式（III）で表されることを特徴とする前記１に記載の着色組成物。 (In the formula, R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom or a substituent. A ₁ , A ₂ , A ₃ and A ₄ each independently represents C—R ₁₅ or a nitrogen atom; ₁₅ represents a hydrogen atom or a substituent, and when a plurality of R ₁₅ are present, each R ₁₅ may be the same or different, J represents an alkylene group, and R ₄ represents an amino group. Or represents an imino group.)

(In the formula, R ₁₂ represents a substituent. R ₁₃ represents an alkyl group having 2 or more carbon atoms, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, or a heterocyclic group. R ₁₆ represents hydrogen. Represents an atom, a methyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a pivaloylamino group, a cyano group or a chloro group , wherein l represents an integer of 1 to 5, and when l is plural, each R ₁₆ is the same However, they may be different, and X represents O, S, SO or SO ₂ .
2. 2. The colored composition as described in 1 above, wherein the general formula (I) is represented by the following general formula (III).

(In the formula, R ₁ , R ₂ , R ₃ , A ₁ , A ₂ , A ₃ and A ₄ represent a group having the same meaning as in formula (I). R ₈ , R ₉ , R ₁₀ and R ₁₁ are each Independently represents a hydrogen atom or an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ₁₀ and R ₁₁ may be linked to each other to form a ring.)

3. A color toner comprising at least one coloring composition as described in 1 or 2 above.
4). An ink jet recording liquid comprising at least one coloring composition as described in 1 or 2 above.
5. 5. An ink jet recording method, wherein the ink jet recording liquid according to 4 is sprayed onto a recording medium for recording.
Moreover, the following aspect is also preferable like this invention.
A. At least one metal chelate dye formed from a dye represented by the general formula (I) or (III), a compound represented by the following general formula (IV), and a metal ion-containing compound comprising metal ions The coloring composition characterized by the above-mentioned.

(In the formula, R ₁₂ represents a substituent. R ₁₃ represents an alkyl group having 2 or more carbon atoms, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, or a heterocyclic group. R ₁₄ represents hydrogen. Represents an atom or a substituent.)
B. At least one metal chelate dye formed from a dye represented by the general formula (I) or (III) and a metal ion-containing compound composed of a compound represented by the general formula (IV) and a metal ion is contained. An ink jet recording liquid.

C. A metal chelate dye comprising: a dye represented by the general formula (I) or (III); and a metal ion-containing compound comprising a compound represented by the general formula (IV) and a metal ion.

The present invention, a novel coloring composition containing the novel metallic chelating dye, even an ink jet recording liquid containing a novel metal chelate dye, an ink jet recording method, it is possible to provide a Karatona chromatography.

  The present invention will be described in more detail. First, the compounds used in the present invention will be described in detail.

In the general formula (I), R ₁ , R ₂ and R ₃ represent a hydrogen atom or a substituent, and examples of the substituent for R ₁ include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an i-propyl group). , T-butyl group, n-dodecyl group, and 1-hexylnonyl group), a cycloalkyl group (such as a cyclopropyl group, a cyclohexyl group, a bicyclo [2.2.1] heptyl group, and an adamantyl group), and Alkenyl groups (for example, 2-propylene group, oleyl group, etc.), aryl groups (for example, phenyl group, ortho-tolyl group, ortho-anisyl group, 1-naphthyl group, 9-anthranyl group, etc.), aralkyl groups (benzyl group, o -Bromobenzyl group etc.), alkynyl group (eg ethynyl group, 1-propynyl group etc.), heterocyclic group (eg 2-tetrahydrofuryl group, 2-thio) Phenyl group, 4-imidazolyl group, 2-pyridyl group, etc.), halogen atom (eg fluorine atom, chlorine atom, bromine atom etc.), cyano group, nitro group, hydroxy group, carbonyl group (eg acetyl group, trifluoroacetyl) Group, alkylcarbonyl group such as pivaloyl group, benzoyl group, pentafluorobenzoyl group, arylcarbonyl group such as 3,5-di-t-butyl-4-hydroxybenzoyl group), oxycarbonyl group (for example, methoxycarbonyl group, An alkoxycarbonyl group such as a cyclohexyloxycarbonyl group and an n-dodecyloxycarbonyl group, an phenoxycarbonyl group, an aryloxycarbonyl group such as a 2,4-di-t-amylphenoxycarbonyl group, a 1-naphthyloxycarbonyl group, and 2- Pyridyloxycarbo Group, heterocyclic oxycarbonyl group such as 1-phenylpyrazolyl-5-oxycarbonyl group, etc.), carbamoyl group (for example, dimethylcarbamoyl group, 4- (2,4-di-t-amylphenoxy) butylaminocarbonyl group, etc.) Alkylcarbamoyl group, phenylcarbamoyl group, arylcarbamoyl group such as 1-naphthylcarbamoyl group), alkoxy group (for example, methoxy group, 2-ethoxyethoxy group, etc.), aryloxy group (for example, phenoxy group, 2,4-di-) t-amylphenoxy group, 4- (4-hydroxyphenylsulfonyl) phenoxy group, etc.), heterocyclic oxy group (eg 4-pyridyloxy group, 2-hexahydropyranyloxy group etc.), carbonyloxy group (eg acetyloxy) Group, trifluoroacetyloxy group, pivaloyl Alkylcarbonyloxy groups such as xy groups, aryloxy groups such as benzoyloxy groups and pentafluorobenzoyloxy groups), urethane groups (eg alkyl urethane groups such as N, N-dimethylurethane groups, N-phenylurethane groups, N Aryl urethane groups such as-(p-cyanophenyl) urethane group), sulfonyloxy groups (for example, methanesulfonyloxy group, trifluoromethanesulfonyloxy group, alkylsulfonyloxy group such as n-dodecanesulfonyloxy group, benzenesulfonyloxy group, arylsulfonyloxy groups such as p-toluenesulfonyloxy group), amino groups (for example, alkylamino groups such as dimethylamino group, cyclohexylamino group, n-dodecylamino group, anilino group, pt-octylanilino group, etc. Arylua Mino group, etc.), sulfonylamino groups (eg methanesulfonylamino group, heptafluoropropanesulfonylamino group, alkylsulfonylamino groups such as n-hexadecylsulfonylamino group, p-toluenesulfonylamino group, pentafluorobenzenesulfonylamino etc. Arylsulfonylamino group), sulfamoylamino group (for example, alkylsulfamoylamino group such as N, N-dimethylsulfamoylamino group, arylsulfamoylamino group such as N-phenylsulfamoylamino group), Acylamino groups (eg alkylcarbonylamino groups such as acetylamino group and myristoylamino group, arylcarbonylamino groups such as benzoylamino group), ureido groups (eg alkylureido groups such as N, N-dimethylaminoureido group) Arylureido groups such as N-phenylureido group, N- (p-cyanophenyl) ureido group), sulfonyl groups (eg alkylsulfonyl groups such as methanesulfonyl group, trifluoromethanesulfonyl group, and aryl such as p-toluenesulfonyl group) Sulfonyl groups), sulfamoyl groups (for example, dimethylsulfamoyl groups, alkylsulfamoyl groups such as 4- (2,4-di-t-amylphenoxy) butylaminosulfonyl group, arylsulfamo groups such as phenylsulfamoyl groups) Moyl group), alkylthio group (eg, methylthio group, t-octylthio group, etc.), arylthio group (eg, phenylthio group, etc.), and heterocyclic thio group (eg, 1-phenyltetrazole-5-thio group, 5-methyl-1, 3,4-oxadiazol-2-thio group, etc.) And the like. These substituents may further have a substituent at a substitutable portion, and examples of the substituent include the examples of the above substituents.

Examples of the substituent for R ₂ are the same as those described for R ₁ above.

Examples of the substituent for R ₃ are the same as those described for R ₁ above.

A ₁ , A ₂ , A ₃ and A ₄ each independently represent C—R ₁₅ or a nitrogen atom, R ₁₅ represents a hydrogen atom or a substituent, and examples of the substituent are the same as those described above for R ₁ . is there.

When there are a plurality of R _{15 s} , each R ₁₅ may be the same or different, and J represents an alkylene group, but the alkylene group may or may not be substituted. It does not have to be. The example of a substituent is synonymous with the description in said R < ₁ >.

R ₄ represents an amino group or an imino group, and an amino group is more preferable. When R ₄ is an amino group, it may be any of primary, secondary, and tertiary amino groups, in which case R ₄ is (A) —NH ₂ , (B) —NHR ₄₁ , (C) —NR. ₄₁ R ₄₂
It is represented by In this case, R ₄₁ and R ₄₂ represent an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ₄₁ and R ₄₂ may be the same or different. R ₄₁ and R ₄₂ may further have a substituent. The example of a substituent is synonymous with the description in said R < ₁ >.

When R ₄ is an imino group, R ₄ is (D) —N═CR ₄₃ R ₄₄
It is represented by In this case, R ₄₃ and R ₄₄ represent a hydrogen atom or a substituent. R ₄₃ and R ₄₄ may be the same or different. R ₄₃ and R ₄₄ may further have a substituent. The example of a substituent is synonymous with the description in said R < ₁ >.

In the general formula (III), R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom or a substituent, and examples of the substituent are the same as those described for R ₁ above.

A ₁ , A ₂ , A ₃ and A ₄ have the same meanings as in the general formula (I).

  In order to use the dye of the general formula (I) or (III) in a so-called thermal transfer type image forming method in which the dye is transferred by heat to obtain an image, the dye needs to have good transferability. In general, the lower the molecular weight of the dye, the better the transferability of the dye. However, even if the molecular weight is too low, a failure such as bleeding over time has occurred. In the present invention, as a result of intensive studies, the inventors have found that there is an optimum value for the molecular weight of the dye. The molecular weight of the dye is preferably 250 to 600, more preferably 300 to 500.

  Specific examples of the dye represented by formula (I) or (III) in the present invention are shown below, but the present invention is not limited thereto.

  The dye of the general formula (I) or (III) used in the present invention can be synthesized mainly by oxidative coupling of a coupler and a color developing agent. For example, in the case of the exemplified compound 66, it can be synthesized according to the following scheme.

In the general formula (IV), R ₁₂ represents a substituent, and examples of the substituent are the same as those in the general formula (I). Preferable examples of R ₁₂ include an alkyl group and an aryl group, more preferably an alkyl group, and most preferably a methyl group. R ₁₃ represents an alkyl group having 2 or more carbon atoms (ethyl group, propyl group, butyl group, octyl group, ethoxyethyl group, isopropyl group, t-butyl group, 2-ethylhexyl group, etc.), cycloalkyl group (for example, cyclohexyl group). , Cycloheptyl group, etc.), alkenyl group (ethenyl group, allyl group, butenyl group, etc.), alkynyl group (ethynyl group, propynyl group, butynyl group, etc.), aryl group (phenyl group, tolyl group, chlorophenyl group, biphenyl group) ), Aralkyl groups (benzyl group, o-bromobenzyl group, etc.), heterocyclic groups (pyrrolyl group, thienyl group, imidazolyl group, furanyl group, pyridinyl group, benzothiazolyl group, thiadiazolyl group, benzothiazolyl group, etc.). These substituents may further have a substituent. Examples of the substituent include a halogen atom (for example, fluorine atom, chlorine atom, bromine atom), an alkyl group (for example, methyl group, ethyl group, propyl group). Butyl group, pentyl group, iso-pentyl group, 2-ethyl-hexyl group, octyl group, decyl group, etc.), cycloalkyl group (for example, cyclohexyl group, cycloheptyl group, etc.), alkenyl group (for example, ethenyl-2) -Propenyl group, 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, etc.), cycloalkenyl group (for example, 1-cycloalkenyl group, 2-cycloalkenyl group) Group), alkynyl group (for example, ethynyl group, 1-propynyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propo group) Si group etc.), alkylcarbonyloxy group (eg acetyloxy group etc.), alkylthio group (eg methylthio group, trifluoromethylthio group etc.), carboxyl group, alkylcarbonylamino group (eg acetylamino group etc.), ureido Group (for example, methylaminocarbonylamino group, etc.), alkylsulfonylamino group (for example, methanesulfonylamino group, etc.), alkylsulfonyl group (for example, methanesulfonyl group, trifluoromethanesulfonyl group, etc.), carbamoyl group (for example, carbamoyl group) N, N-dimethylcarbamoyl group, N-morpholinocarbonyl group, etc.), sulfamoyl group (sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfamoyl group, etc.), trifluoromethyl group, hydroxyl group, Toro group, cyano group, alkylsulfonamide group (for example, methanesulfonamide group, butanesulfonamide group, etc.), alkylamino group (for example, amino group, N, N-dimethylamino group, N, N-diethylamino group, etc.), Sulfo group, phosphono group, sulfite group, sulfino group, alkylsulfonylaminocarbonyl group (for example, methanesulfonylaminocarbonyl group, ethanesulfonylaminocarbonyl group, etc.), alkylcarbonylaminosulfonyl group (for example, acetamidosulfonyl group, methoxyacetamidosulfonyl) Group), alkynylaminocarbonyl group (eg, acetamidocarbonyl group, methoxyacetamidocarbonyl group, etc.), alkylsulfinylaminocarbonyl group (eg, methanesulfinylaminocarbonyl group) , Ethanesulfinylaminocarbonyl group etc.), aryl group (eg phenyl group, carboxyphenyl group etc.), aryloxy group (phenoxy group, p-chlorophenoxy group, p-tert-butylphenoxy group etc.), heterocyclic group ( A pyrrolyl group, a thienyl group, an imidazolyl group, a furanyl group, a pyridinyl group, a benzothiazolyl group, a thiadiazolyl group, a benzothiazolyl group, etc.). Moreover, when there are two or more substituents, they may be the same or different.

R ₁₄ represents a hydrogen atom or a substituent, and examples of the substituent include the substituent of R ₁₃ described above.

  Furthermore, the compound represented by the general formula (IV) is preferably a compound represented by the following general formula (V).

In the general formula (V), R ₁₂ and R ₁₃ represent a group having the same meaning as in the general formula (IV), and R ₁₆ represents a group having the same meaning as in the general formula (I). l represents an integer of 1 to 5. When l is plural, each R ₁₆ may be the same or different. X represents O, S, SO or SO ₂ .

  In order for the compound of the general formula (IV) or (V) to form a metal-containing compound and to exhibit a preferable performance, the hydrophilicity / hydrophobicity parameter value (LogP value) of the compound represented by the general formula (IV) is 4 The range is preferably from 0 to 12.0, and more preferably from 5.0 to 11.0.

  LogP, which is a parameter representing hydrophobicity / hydrophilicity, can usually be obtained from the distribution coefficient of a substance in two solvent systems to n-octanol and water. (Nan-Edo), pages 73-103. In recent years, a method for obtaining logP by calculation has been proposed. As a particularly useful method, software “CHEMLAB-II Revision 10.02” of Molecular Design Limited, USA can be mentioned. In the present invention, logP is a value calculated using this software “CHEMLAB-II Revision 10.02.”

  Specific examples of the compound represented by the general formula (II) or (IV) are shown below, but the present invention is not limited thereto.

  Next, the metal ion-containing compound used in the present invention will be described. The metal ion-containing compound used in the present invention is represented by the following general formula (A).

Formula (A) M ^{n +} (X ⁻ ) _n
M ^{n +} represents an n-valent metal ion, and among these, a divalent metal ion is preferred from the color of the metal ion-containing compound and the color tone of the chelated dye, and among these, nickel, copper and zinc are preferred. X ⁻ represents an anionized form of the general formula (II) or (IV) capable of forming a complex with an n-valent metal ion. Further, the metal ion-containing compound used in the present invention may have a neutral ligand depending on the central metal, and typical examples of the ligand include H ₂ O or NH ₃ .

  The metal ion-containing compound in the present invention is preferably one that can be reacted with an n-valent metal compound after the compound of general formula (II) or (IV) is synthesized. The method for synthesizing these metal ion-containing compounds can be synthesized according to the method described in “Chelate Chemistry (5) Complex Chemistry Experimental Method [I] (Edited by Nanedo)”. Metal compounds used include nickel chloride, nickel acetate, magnesium compounds typified by magnesium chloride, calcium compounds typified by calcium chloride, barium chloride, zinc chloride, zinc acetate, titanium (II) chloride, iron chloride ( II), copper acetate, copper (II) chloride, cobalt chloride, manganese chloride (II), lead chloride, lead acetate, mercury chloride, mercury acetate, etc. As mentioned above, the color and chelate of metal ion-containing compounds From the viewpoint of the color tone of the converted pigment, copper acetate, zinc chloride, zinc acetate, nickel chloride and nickel acetate are preferred, and nickel acetate is most preferred.

  Next, the synthesis example of a metal ion containing compound is shown.

Synthesis Example 1 (Synthesis of Compound IV-8)
In 45 ml of acetonitrile, a 9 ml aqueous solution of 7.9 g (0.04299 mol) of 3-oxo-butyric acid-n-hexyl ester and 9.4 g (0.08458 mol) of calcium chloride and 12.8 g (0.1269 mol) of triethylamine ) Was added and stirred for 1 hour, and then 11.3 g (0.04440 mol) of 4- (4-tert-butylphenoxy) butyric chloride was added dropwise over about 20 minutes while maintaining the internal temperature at 30-35 ° C. After the addition, the mixture was further stirred for 2 hours, and then the reaction solution was washed with water and concentrated. Purification was performed by column chromatography (hexane / ethyl acetate) to obtain 13.3 g (yield 78.3%) of compound IV-8. The structure was identified using ¹ H-NMR and mass spectrum.

Synthesis Example 2 (Synthesis of Compound IV-19)
A reaction, post-treatment with the same formulation except that 6.8 g (0.04299 mol) of 3-oxo-butyric acid-n-butyl ester was used instead of 3-oxo-butyric acid-n-hexyl ester of Synthesis Example 1. Purification was performed to obtain 16.0 g (yield: 85.9%) of compound IV-19.

Synthesis Example 3 (Synthesis of Compound IV-22)
The reaction was carried out in the same manner except that 9.3 g (0.03953 g) of 3-oxo-butyric acid-4-tert-butylphenyl ester was used instead of 3-oxo-butyric acid-n-hexyl ester of Synthesis Example 1. Treatment and purification were performed to obtain 14.6 g (yield: 81.6%) of compound IV-22.

Synthesis Example 4 (Synthesis of Compound IV-47)
14.0 g of 3-oxo-butyric acid-iso-hexadecyl ester instead of 3-oxo-butyric acid-n-hexyl ester of Synthesis Example 1 and 4- (4-tert-butylphenoxy) butyric acid chloride instead of 4- Except for using 9.9 g of (4-cyanophenoxy) butyric acid chloride, reaction, post-treatment and purification were carried out in the same manner to obtain 18.3 g of Compound IV-47 (yield 83.0%).

Synthesis Example 5 (Synthesis of metal ion-containing compound VI-8)
After dissolving 3.2 g (0.01305 mol) of nickel acetate tetrahydrate in 30 ml of methanol, 10.6 g (0.02611 mol) of Compound IV-8 was added dropwise over 5 minutes. After reacting at room temperature for 1 hour, the mixture was ice-cooled for about 2 hours, and the precipitated crystals were collected by filtration. The crystals were washed with heptane and recrystallized from about 120 ml of methanol to obtain 8.6 g (yield 76.2%) of metal ion-containing compound VI-8. The melting point was 67-62 ° C.

Synthesis Example 6 (Synthesis of metal ion-containing compound VII-8)
The reaction, post-treatment and purification were performed in the same manner as in Synthesis Example 5 except that copper acetate monohydrate was used instead of the nickel acetate tetrahydrate of Synthesis Example 5, and 7.6 g of metal ion-containing compound VII-8 was obtained. (Yield: 68.3%) was obtained. The melting point was 71-73 ° C.

Synthesis Example 7 (Synthesis of metal ion-containing compound VI-19)
The reaction, post-treatment and purification were performed in the same manner as in Synthesis Example 5 except that 11.3 g (0.02611 mol) of Compound IV-19 was used instead of Compound IV-8 of Synthesis Example 5, and metal ion-containing compound VI- 11.3 g (yield 94.0%) of 19 was obtained. The melting point was 65-67 ° C.

Synthesis Example 8 (Synthesis of metal ion-containing compound VI-47)
The reaction, post-treatment and purification were carried out in the same manner as in Synthesis Example 5 except that 18.3 g (0.03562 mol) of Compound IV-47 was used instead of Compound IV-8 in Synthesis Example 5, and metal ion-containing compound VI- 19.1 g (yield 93.8%) of 19 was obtained. The melting point was 64-69 ° C.

  Table 1 below shows a list of metal ion-containing compounds prepared in the same manner.

  The dye represented by the general formula (I) or (III) can react with a metal ion-containing compound to form a metal chelate dye.

  Examples of the metal ion-containing compound include inorganic or organic salts and metal complexes of metal ions, and among them, salts and complexes of organic acids are preferable.

Examples of the metal include monovalent and polyvalent metals belonging to Groups V to VIII of the periodic table, among which Al, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Sn, Ti and Zn is preferable, and Ni, Cu, Cr, Co and Zn are particularly preferable. Specific examples of the metal ion-containing compound include salts of Ni ²⁺ , Cu ²⁺ , Cr ²⁺ , Co ²⁺ and Zn ²⁺ with aliphatic acids such as acetic acid and stearic acid, benzoic acid, salicylic acid, etc. And salts thereof with aromatic carboxylic acids. Moreover, the complex represented by the following general formula (VIII) can be particularly preferably used.

General formula (VIII) [M (Q ₁ ) _a (Q ₂ ) _b (Q ₃ ) _c ] _p ⁺ (Y ⁻ ) _p
In the formula, M represents a metal ion, preferably Ni ²⁺ , Cu ²⁺ , Cr ²⁺ , Co ²⁺ , Zn ²⁺ .

Q ₁ , Q ₂ , and Q ₃ each represent a coordination compound that can be coordinated to a metal ion represented by M, and may be the same or different from each other. These coordination compounds can be selected from, for example, coordination compounds described in Chelate Science (5) (Nan Edo).

Y ^- is represents an organic anion group, and specific examples thereof include tetraphenyl boron anion and alkylbenzene sulfonate anion.

a represents 1, 2 or 3; b represents 1, 2 or 0; c represents 1 or 0; in these, the complex represented by the general formula (VIII) is tetradentate or hexadentate. Or the number of ligands of Q ₁ , Q ₂ , and Q ₃ .

  p represents 0, 1 or 2. p = 0 indicates that the coordination compound represented by Q is an anionic compound, and the anionic compound represented by Q and the metal cation represented by M are electrically neutralized. means.

  As the anionic compound, a compound represented by the general formula (II) or (IV) is preferable, and a compound represented by the general formula (IV) is particularly preferable.

  Next, the metal chelate dye of the present invention will be described. The metal chelate dye of the present invention is not particularly limited as long as the compound represented by the general formula (I) or (III) is a ligand, but preferably the metal complex represented by the general formula (VIII) and the general formula A metal chelate dye comprising the compound represented by (I) or (III). A preferred example of the metal complex represented by the general formula (VIII) is a metal ion-containing compound comprising a compound represented by the general formula (II) or (IV) and a metal ion, and more preferably represented by the general formula (IV). It is a metal ion containing compound which consists of a compound represented and a metal ion.

  Preferred examples of the metal chelate dye of the present invention are represented by the following general formula 1 or 2.

  In the general formulas 1 and 2, the substituents have the same meanings as described in the general formulas (I), (III), and (IV), respectively.

M ²⁺ represents a divalent metal ion. Among these, nickel, copper and zinc are preferable from the viewpoint of the color of the metal ion-containing compound itself and the color tone of the chelated dye.

  Specific examples of chelate dyes represented by general formula 1 or general formula 2 are shown below. The present invention is not limited to these.

  The metal chelate dye of the present invention is synthesized from a dye represented by the general formula (I) or (III), a compound represented by the general formula (II) or (IV), and a metal ion-containing compound composed of a metal ion. Can do.

  In the present invention, the dye used other than the dye represented by the general formula (I) or (III) is not particularly limited, but is preferably represented by the following general formula (1), (2) and general formula (4). Dyes to be used.

In the formula, each of R ₁₁₁ and R ₁₁₂ represents a hydrogen atom or a substituent, R ₁₁₃ represents an alkyl group or an aryl group which may have a substituent, and Z is a 5- to 6-membered member together with 2 carbon atoms. Represents an atomic group necessary for constituting the aromatic ring.

Examples of the substituent represented by R ₁₁₁ and R ₁₁₂ in the general formula (1) include, for example, a halogen atom, an alkyl group (an alkyl group having 1 to 12 carbon atoms, linked by an oxygen atom, a nitrogen atom, a sulfur atom, or a carbonyl group). Or a aryl group, alkenyl group, alkynyl group, hydroxyl group, amino group, nitro group, carboxyl group, cyano group or halogen atom may be substituted, for example, methyl, isopropyl, t -Butyl, trifluoromethyl, methoxymethyl, 2-methanesulfonylethyl, 2-methanesulfonamidoethyl, cyclohexyl, etc.), aryl groups (eg phenyl, 4-tert-butylphenyl, 3-nitrophenyl, 3-acylaminophenyl) , 2-methoxyphenyl, etc.), cyano group, alkoxyl group, aryloxy Group, acylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, Examples include an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a phosphonyl group, and an acyl group.

The alkyl group and aryl group represented by R _113, can be the same as the alkyl group, an aryl group represented by R ₁₁₁ and R _112.

Specific examples of the 5- to 6-membered aromatic ring formed with two carbon atoms represented by Z include benzene, pyridine, pyrimidine, triazine, pyrazine, pyridazine, pyrrole, furan, thiophene, pyrazole, and imidazole. , Triazole, oxazole, thiazole and the like, and these rings may further form a condensed ring with another aromatic ring. These rings may have a substituent, and examples of the substituent include the same substituents represented by R ₁ .

  The dye represented by the general formula (1) used in the present invention may be a compound represented by the following general formula (B), for example, Chemical Reviews, Vol. 75, 241 (1975), and can be produced according to a known coupling reaction with a compound represented by the following general formula (C).

Wherein, R _111, R _112, R ₁₁₃ and Z have the same meanings as R _111, R _112, R ₁₁₃ and Z of each of the general formula (1).

  Specific examples of the dye represented by the general formula (1) include compound Nos. Described in paragraph Nos. 0065 to 0067 of JP-A No. 2004-74617. Examples thereof include dyes Y-1 to Y23 described in (1) -1 to (1) -32 and paragraph numbers 0023 to 0025 of JP-A-5-177958.

In the formula, R ₁₂₁ represents a hydrogen atom, a halogen atom or a monovalent substituent, and R ₁₂₂ represents an _optionally substituted aromatic carbocyclic group or aromatic heterocyclic group. X represents a methine group or a nitrogen atom. R ₁₂₃ represents the following general formula (3), Y represents an atomic group forming a nitrogen-containing aromatic heterocyclic ring, and X ₁ represents a carbon atom or a nitrogen atom.

In the general formula (2), R ₁₂₁ represents a hydrogen atom, a halogen atom (fluorine, chlorine, etc.) or a monovalent substituent, and the monovalent substituent may be an alkyl group or aryl group which may be further substituted, respectively. , Aromatic heterocyclic group, acyl group, amino group, nitro group, cyano group, acylamino group, alkoxy group, hydroxyl group, alkoxycarbonyl group and the like.

R ₁₂₂ represents an optionally substituted aromatic carbocyclic group or aromatic heterocyclic group, preferably benzene ring, pyridine ring, pyrimidine ring, furan ring, thiophene ring, thiazole ring, imidazole ring, naphthalene ring, etc. Residue. These ring residues may form a condensed ring with another carbocyclic ring (for example, benzene ring) or heterocyclic ring (for example, pyridine ring). Examples of the substituent on the ring include an alkyl group, aryl group, acyl group, amino group, nitro group, cyano group, acylamino group, alkoxy group, hydroxyl group, alkoxycarbonyl group, halogen atom, and the like. May be substituted. X represents a methine group or a nitrogen atom.

_R123 represents the general formula (3). This general formula (3) represents a nitrogen-containing aromatic heterocyclic residue which may have a substituent. Examples of the heterocyclic ring include pyrazole, imidazole, oxazole, thiazole, isoxazole, triazole, pyridine, pyridazine, and pyrimidine. Pyrazine, triazine, benzimidazole, benzothiazole, benzoxazole, quinoline, isoquinoline and the like are preferable. These rings may further form a condensed ring with another carbocyclic ring (for example, a benzene ring) or a heterocyclic ring (for example, a pyridine ring).

Examples of substituents on the ring include alkyl groups, aryl groups, acyl groups, amino groups, nitro groups, cyano groups, acylamino groups, alkoxy groups, hydroxyl groups, alkoxycarbonyl groups, halogen atoms, and the like. May be further substituted. X ₁ represents a carbon atom or a nitrogen atom.

  Y represents an atomic group that forms a nitrogen aromatic heterocycle, preferably an atomic group that forms a 5- or 6-membered double nitrogen aromatic heterocycle, and the ring may further have a substituent. Good.

Preferred examples of the substituent on the ring include preferred examples of _R122 .

  The dye represented by the general formula (2) used in the present invention can be synthesized according to a conventionally known method. For example, the azomethine dye in the general formula (2) can be synthesized according to the oxidative coupling method described in each specification of JP-A-63-113077, JP-A-3-275767, and 4-89287. I can do it.

  Specific examples of the dye represented by the general formula (2) include dyes (2) -1 to (2) -38 and JP-A No. 9-104 described in paragraph numbers 0074 to 0078 of JP-A-2004-74617. Examples include dyes III-1 to III-38 described in paragraphs 0026 to 0028 of No. 226259.

In the formula, each of R ₁₃₁ and R ₁₃₂ represents a substituted or unsubstituted aliphatic group, and R ₁₃₃ represents a substituent. n represents an integer of 0 to 4, and when n is 2 or more, the plurality of R ₁₃₃ may be the same or different. R ₁₃₄ , R ₁₃₅ and R ₁₃₆ all represent an alkyl group. At this time, R ₁₃₄ , R ₁₃₅ and R ₁₃₆ may be the same or different. R ₁₃₅ and R ₁₃₆ are alkyl groups having 3 to 8 carbon atoms.

In the general formula (4), R ₁₃₁ and R ₁₃₂ represent a substituted or unsubstituted aliphatic group, and R ₁₃₁ and R ₁₃₂ may be the same or different. Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, and the like. Examples of the group that can replace these alkyl groups include a linear or branched alkyl group (for example, a methyl group, Ethyl group, i-propyl group, t-butyl group, n-dodecyl group, 1-hexylnonyl group and the like), cycloalkyl group (for example, cyclopropyl group, cyclohexyl group, bicyclo [2.2.1] heptyl group, And adamantyl group, etc.), and alkenyl groups (eg 2-propylene group, oleyl group etc.), aryl groups (eg phenyl group, ortho-tolyl group, ortho-anisyl group, 1-naphthyl group, 9-anthranyl group etc.), Heterocyclic groups (for example, 2-tetrahydrofuryl group, 2-thiophenyl group, 4-imidazolyl group, 2-pyridyl group, etc.), Gen atom (for example, fluorine atom, chlorine atom, bromine atom), cyano group, nitro group, hydroxy group, carbonyl group (for example, alkylcarbonyl group such as acetyl group, trifluoroacetyl group, pivaloyl group, benzoyl group, pentafluorobenzoyl) Group, arylcarbonyl group such as 3,5-di-t-butyl-4-hydroxybenzoyl group), oxycarbonyl group (for example, alkoxycarbonyl group such as methoxycarbonyl group, cyclohexyloxycarbonyl group, n-dodecyloxycarbonyl group) Aryloxycarbonyl groups such as phenoxycarbonyl group, 2,4-di-t-amylphenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-pyridyloxycarbonyl group, 1-phenylpyrazolyl-5-oxycarbonyl group, etc. of Oxycyclic carbonyl group), carbamoyl group (for example, dimethylcarbamoyl group, alkylcarbamoyl group such as 4- (2,4-di-t-amylphenoxy) butylaminocarbonyl group, phenylcarbamoyl group, 1-naphthylcarbamoyl group, etc. Arylcarbamoyl group), alkoxy group (for example, methoxy group, 2-ethoxyethoxy group, etc.), aryloxy group (for example, phenoxy group, 2,4-di-t-amylphenoxy group, 4- (4-hydroxyphenylsulfonyl)) Phenoxy group etc.), heterocyclic oxy group (eg 4-pyridyloxy group, 2-hexahydropyranyloxy group etc.), carbonyloxy group (eg acetyloxy group, trifluoroacetyloxy group, pivaloyloxy group etc.) Group, benzoyloxy group, Aryl urethane groups such as n-fluorobenzoyloxy group), urethane groups (eg, alkyl urethane groups such as N, N-dimethylurethane group, aryl urethanes such as N-phenylurethane group, N- (p-cyanophenyl) urethane group) Group), a sulfonyloxy group (for example, an alkylsulfonyloxy group such as methanesulfonyloxy group, trifluoromethanesulfonyloxy group, n-dodecanesulfonyloxy group, arylsulfonyloxy group such as benzenesulfonyloxy group, p-toluenesulfonyloxy group) Amino groups (for example, alkylamino groups such as dimethylamino group, cyclohexylamino group, n-dodecylamino group, arylamino groups such as anilino group, pt-octylanilino group, etc.), sulfonylamino groups (for example, methanesulfonyl) amino , Alkylsulfonylamino groups such as heptafluoropropanesulfonylamino group and n-hexadecylsulfonylamino group, arylsulfonylamino groups such as p-toluenesulfonylamino group and pentafluorobenzenesulfonylamino), sulfamoylamino groups (for example, N , Alkylsulfamoylamino groups such as N-dimethylsulfamoylamino group, arylsulfamoylamino groups such as N-phenylsulfamoylamino group), acylamino groups (eg alkyl such as acetylamino group and myristoylamino group) Arylcarbonylamino group such as carbonylamino group, benzoylamino group), ureido group (for example, alkylureido group such as N, N-dimethylaminoureido group, N-phenylureido group, N- (p-cyanophenyl) ureido Arylsulfide groups such as methanesulfonyl group, alkylsulfonyl groups such as trifluoromethanesulfonyl group, and arylsulfonyl groups such as p-toluenesulfonyl group), sulfamoyl groups (such as dimethylsulfamoyl group, 4- (2,4-di-t-amylphenoxy) alkylsulfamoyl groups such as butylaminosulfonyl group, arylsulfamoyl groups such as phenylsulfamoyl group), alkylthio groups (for example, methylthio group, t-octylthio group, etc.) ), An arylthio group (for example, phenylthio group), and a heterocyclic thio group (for example, 1-phenyltetrazol-5-thio group, 5-methyl-1,3,4-oxadiazole-2-thio group). Can be mentioned.

  Examples of the cycloalkyl group and the alkenyl group are the same as the above substituents. Examples of the alkynyl group include 1-propyne, 2-butyne, 1-hexyne and the like.

It is also preferred that R ₁₃₁ and R _{132 form} a non-aromatic cyclic structure (eg, pyrrolidine ring, piperidine ring, morpholine ring, etc.).

R ₁₃₃ is preferably an alkyl group, a cycloalkyl group, an alkoxy group or an acylamino group among the above substituents. n represents an integer of 0 to 4, and when n is 2 or more, the plurality of R ₁₃₃ may be the same or different.

_R134 is an alkyl group, and examples thereof include a methyl group, an ethyl group, an i-propyl group, a t-butyl group, an n-dodecyl group, and a 1-hexylnonyl group. R ₁₃₄ is preferably a secondary or tertiary alkyl group, and examples of a preferable secondary or tertiary alkyl group include an isopropyl group, a sec-butyl group, a tert-butyl group, and a 3-heptyl group. The most preferred substituent for R ₁₃₄ is an isopropyl group or a tert-butyl group. The alkyl group of R ₁₃₄ may be substituted, but is all substituted with a substituent consisting of a carbon atom and a hydrogen atom, and is not substituted with a substituent containing other atoms.

R ₁₃₅ is an alkyl group, and examples thereof include an n-propyl group, an i-propyl group, a t-butyl group, an n-dodecyl group, and a 1-hexylnonyl group. R ₁₃₅ is preferably a secondary or tertiary alkyl group, and examples of a preferable secondary or tertiary alkyl group include an isopropyl group, a sec-butyl group, a tert-butyl group, and a 3-heptyl group. The most preferred substituent for R ₁₃₅ is an isopropyl group or a tert-butyl group. The alkyl group of R ₁₃₅ may be substituted, but is all substituted with a substituent consisting of a carbon atom and a hydrogen atom, and is not substituted with a substituent containing other atoms.

_R136 represents an alkyl group, and examples thereof include n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, isopropyl group, sec-butyl group, tert-butyl group. , 3-heptyl group and the like. Particularly preferred substituents for R ₁₃₆ are straight-chain alkyl groups having 3 or more carbon atoms, and examples thereof include n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, and n-heptyl group. And most preferably an n-propyl group or an n-butyl group. The alkyl group of R ₁₃₆ may be substituted, but is all substituted with a substituent consisting of a carbon atom and a hydrogen atom, and is not substituted with a substituent containing other atoms.

  The dye represented by the general formula (4) used in the present invention can be synthesized according to a conventionally known method. For example, it can synthesize | combine according to the oxidative coupling method as described in each specification, such as Unexamined-Japanese-Patent No. 2001-334755, Unexamined-Japanese-Patent No. 2002-234266.

  Specific examples of the dye represented by the general formula (4) include dyes (4) -1 to (4) -36 described in paragraph Nos. 0088 to 0093 of JP-A No. 2004-74617, and JP-A No. 2004-74617. Examples thereof include dyes 1-36 described in 2002-234266.

Next, the colored composition of the present invention will be described. The colored composition of the present invention is a colored composition containing a metal chelate dye having the dye represented by formula (I) or (III) as a ligand. If it is, there will be no restriction | limiting in particular, More preferably, it is the colored composition containing the metal chelate pigment | dye formed from the compound represented by general formula (IV) and the metal ion containing compound which consists of metal ions.

  It is known that a metal chelate dye formed of a dye and a metal has excellent performance in light resistance and wet heat fastness compared to a dye before chelation. Furthermore, chelating with a metal may cause a change in the spectral absorption characteristics of the dye. For example, the molar extinction coefficient increases, and there is a merit in color reproduction such that sharpening provides a good hue.

  Next, the ink jet recording liquid, ink jet recording method, color toner, and color filter of the present invention will be described in detail.

  The ink jet recording liquid containing the coloring composition of the present invention may be one using only one kind of the coloring composition of the present invention, or may be a combination of two or more kinds of coloring compositions. It may be used in combination with a coloring composition outside the present invention.

  The ink jet recording liquid containing the coloring composition of the present invention can use various solvent systems such as an aqueous solvent, an oil-based solvent, and a solid (phase change) solvent, and the effects of the present invention are particularly effective when an aqueous solvent is used. Demonstrate.

  As the aqueous solvent, water (for example, ion-exchanged water is preferable) and a water-soluble organic solvent are generally used.

  Examples of water-soluble organic solvents include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, benzyl alcohol, etc.), polyhydric alcohols (eg, ethylene glycol, diethylene glycol) , Triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol ethers (eg, ethylene glycol monomethyl ether) , Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol Monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether, propylene glycol Monophenyl ether, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine) The Ethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclics (eg, 2-pyrrolidone, N-methyl) -2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (eg dimethyl sulfoxide etc.), sulfones (eg sulfolane etc.), urea, acetonitrile, acetone Etc.

  The aqueous solvent as described above can be used by dissolving it as it is if the colored composition of the present invention is soluble in the solvent system.

  On the other hand, when the colored composition of the present invention is insoluble in the solvent system as it is, the colored composition is mixed with various dispersing machines (for example, ball mill, sand mill, attritor, roll mill, agitator mill, Henschel mixer, colloid mill, Use an ultrasonic homogenizer, pearl mill, jet mill, ang mill, etc.) or disperse the coloring composition in a soluble organic solvent and then disperse it in the solvent system together with the polymer dispersant and surfactant. Can be made. Furthermore, when it is an insoluble liquid or a semi-molten product as it is, it can be dissolved in an organic solvent as it is or in a soluble state and can be dispersed in the solvent system together with a polymer dispersant or a surfactant.

  When the colored composition of the present invention is insoluble in the solvent system, it is preferably finely divided and dispersed in the solvent system, and more preferably dispersed in fine particles having an average particle size of 150 nm or less. .

  The average particle diameter is a volume average particle diameter, and a circle-converted average particle diameter obtained from an average value of projected areas (determined for at least 100 particles) of a transmission electron microscope (TEM) photograph is spherical. Obtained by conversion. The coefficient of variation can be obtained by determining the volume average particle size and its standard deviation and dividing the standard deviation by the volume average particle size. Alternatively, the volume average particle diameter and its standard deviation can be obtained by using a dynamic light scattering method. For example, it can be obtained using a laser particle size analysis system manufactured by Otsuka Electronics or a Zetasizer manufactured by Malvern.

  Moreover, after dissolving a coloring composition in the organic solvent in which the coloring composition of this invention is soluble, it is preferable to make it disperse | distribute to an aqueous solvent with oil-soluble polymer as a fine particle dispersion.

  Specific methods for preparing the aqueous solvent used for such an ink jet recording liquid are disclosed in, for example, JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, and 7- Reference can be made to the method described in Japanese Patent No. 118584.

  Next, the oil-soluble polymer will be described.

  There is no restriction | limiting in particular as said oil-soluble polymer, Although it can select suitably according to the objective, A vinyl polymer is mentioned suitably. Examples of the vinyl polymer include conventionally known ones, which may be any of a water-insoluble type, a water-dispersed (self-emulsifying) type, and a water-soluble type. In view of the above, a water dispersion type is preferable.

  The water-dispersible vinyl polymer may be any of an ion dissociation type, a non-ionic dispersible group-containing type, or a mixture thereof.

  Examples of the ion dissociation type vinyl polymer include a vinyl polymer containing a cationic dissociable group such as a tertiary amino group, and a vinyl polymer containing an anionic dissociable group such as a carboxylic acid and a sulfonic acid. . Examples of the nonionic dispersible group-containing vinyl polymer include vinyl polymers containing a nonionic dispersible group such as a polyethyleneoxy chain. Among these, from the viewpoint of dispersion stability of the colored fine particles, an ion dissociation type vinyl polymer containing an anionic dissociable group, a nonionic dispersible group containing type vinyl polymer, and a mixed type vinyl polymer are preferable.

  As a monomer which forms the said vinyl polymer, the following are mentioned, for example. That is, acrylic esters, specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chloro Cyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahi Rofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, glycidyl acrylate, 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, 2,2 , 2-tetrafluoroethyl acrylate, 1H, 1H, 2H, 2H-perfluorodecyl acrylate and the like.

  Methacrylic acid esters, specifically, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate , Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate 4-Hido Xylbutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, allyl methacrylate, glycidyl methacrylate, 2,2,2-tetrafluoroethyl methacrylate, 1H, 1H, 2H, 2H-perfluorodecyl methacrylate Such as over doors and the like.

  Vinyl esters, specifically vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, etc. Is mentioned.

  Acrylamides, specifically, acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, tert-butyl acrylamide, tert-octyl acrylamide, cyclohexyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, methoxymethyl acrylamide, butoxymethyl acrylamide, Examples include methoxyethyl acrylamide, phenyl acrylamide, dimethyl acrylamide, diethyl acrylamide, β-cyanoethyl acrylamide, N- (2-acetoacetoxyethyl) acrylamide, diacetone acrylamide, and the like.

  Methacrylamide, specifically, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacryl Examples include amide, phenylmethacrylamide, dimethylmethacrylamide, β-cyanoethylmethacrylamide, N- (2-acetoacetoxyethyl) methacrylamide.

  Olefins, specifically dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene, styrenes such as styrene Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, vinyl benzoic acid methyl ester and the like.

  Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  Other monomers include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl Vinyl ketone, methoxyethyl vinyl ketone, N-vinyl oxazolidone, N-vinyl pyrrolidone, vinylidene chloride, methylene malonnitrile, vinylidene, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyl Examples thereof include oxyethyl phosphate and dioctyl-2-methacryloyloxyethyl phosphate.

  Examples of the monomer having a dissociable group include a monomer having an anionic dissociable group and a monomer having a cationic dissociable group.

  Examples of the monomer having an anionic dissociable group include a carboxylic acid monomer, a sulfonic acid monomer, and a phosphoric acid monomer.

  Examples of the carboxylic acid monomer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, crotonic acid, itaconic acid monoalkyl esters (for example, itaconic acid monomethyl, itaconic acid monoethyl, itaconic acid monobutyl, etc. ), Maleic acid monoalkyl esters (for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.).

  Examples of the sulfonic acid monomer include styrene sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid (for example, acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid, etc.), methacryloyloxyalkyl sulfonic acid. (For example, methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.), acrylamide alkylsulfonic acid (for example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfone, etc.) Acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.), methacrylamide alkylsulfonic acid (for example, 2-methacrylic acid) 2-methyl-ethanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylbutanesulfonic acid).

  Examples of the phosphoric acid monomer include vinylphosphonic acid and methacryloyloxyethylphosphonic acid.

  Among these, acrylic acid, methacrylic acid, styrene sulfonic acid, vinyl sulfonic acid, acrylamide alkyl sulfonic acid, and methacrylamide alkyl sulfonic acid are preferable. Acrylic acid, methacrylic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfone Acid, 2-acrylamido-2-methylbutanesulfonic acid is more preferable.

  Examples of the monomer having a cationic dissociable group include monomers having a tertiary amino group such as dialkylaminoethyl methacrylate and dialkylaminoethyl atacrylate.

  Examples of the monomer containing a nonionic dispersible group include an ester of polyethylene glycol monoalkyl ether and a carboxylic acid monomer, an ester of polyethylene glycol monoalkyl ether and a sulfonic acid monomer, polyethylene glycol monoalkyl ether and phosphorus. Examples thereof include an ester with an acid monomer, a vinyl group-containing urethane formed from a polyethylene glycol monoalkyl ether and an isocyanate group-containing monomer, and a macromonomer containing a polyvinyl alcohol structure. As a repeating number of the ethyleneoxy part of the said polyethylene glycol monoalkyl ether, 8-50 are preferable and 10-30 are more preferable. The number of carbon atoms in the alkyl group of the polyethylene glycol monoalkyl ether is preferably 1-20, and more preferably 1-12.

  These monomers may be used alone to form a vinyl polymer, or two or more may be used in combination to form a vinyl polymer. The purpose of the vinyl polymer (Tg adjustment, dissolution) Improvement, dispersion stability, etc.).

  The oil-based solvent used in the present invention uses an organic solvent. Examples of oil-based solvents include alcohols (eg, pentanol, heptanol, octanol, phenylethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, anis alcohol, etc.), esters (ethylene glycol diacetate, ethylene glycol monomethyl). Ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol diacetate, ethyl acetate, amyl acetate, benzyl acetate, phenylethyl acetate, phenoxyethyl acetate, ethyl phenylacetate, benzyl propionate, ethyl benzoate, butyl benzoate, butyl laurate, Isopropyl myristate, triethyl phosphate, tributyl phosphate, diethyl phthalate, dibutyl phthalate, diethyl malonate, dip dimalonate Pill, diethyl diethylmalonate, diethyl succinate, dibutyl succinate, diethyl glutarate, diethyl adipate, dipropyl adipate, dibutyl adipate, di (2-methoxyethyl) adipate, diethyl sebacate, diethyl maleate, maleate Dibutyl acid, dioctyl maleate, diethyl fumarate, dioctyl fumarate, cinnamic acid-3-hexenyl, etc.), ethers (eg, butyl phenyl ether, benzyl ethyl ether, hexyl ether, etc.), ketones (eg, benzyl methyl) Ketones, benzylacetone, diacetone alcohol, cyclohexanone, etc.), hydrocarbons (eg petroleum ether, petroleum benzyl, tetralin, decalin, tertiary amylbenzene, dimethylnaphthalene, etc.), amides (eg , N, N-diethyldodecanamide, etc.).

  The oil-based solvent as described above can be used by dissolving the colored composition of the present invention as it is, and can also be used by dispersing or dissolving in combination with a resinous dispersant or a binder.

  For the specific method for preparing the oil-based solvent used in such an ink jet recording liquid, the methods described in JP-A-3-231975 and JP-A-5-508883 can be referred to.

  The solid (phase change) solvent used in the present invention is a phase change solvent that is a solid at room temperature as a solvent and is in a molten liquid state when the inkjet recording liquid is heated and jetted.

  Such phase change solvents include natural waxes (eg, beeswax, carnauba wax, rice wax, wood wax, jojoba oil, whale wax, candelilla wax, lanolin, montan wax, ozokerite, ceresin, paraffin wax, microwax. Crystallin wax, petrolactam, etc.), polyethylene wax derivatives, chlorinated hydrocarbons, organic acids (eg palmitic acid, stearic acid, behenic acid, tiglic acid, 2-acetonaphthone behenic acid, 12-hydroxystearic acid, dihydroxystearic acid) Acid), organic acid esters (for example, esters of the above-mentioned organic acids with alcohols such as glycerin, diethylene glycol, and ethylene glycol), alcohols (for example, dodecanol, tetradecanol, hexadecanol, eicosano) , Docosanol, tetracosanol, hexacosanol, octacosanol, dodecenol, myricyl alcohol, tetracenol, hexadecenol, eicosenol, docosenol, pinene glycol, hinokiol, butynediol, nonanediol, isophthalyl alcohol, mesythelin, teleaphthalyl alcohol , Hexanediol, decanediol, dodecanediol, tetradecandiol, hexadecanediol, docosandiol, tetracosanediol, tvneol, phenylglycerin, eicosanediol, octanediol, phenylpropylene glycol, bisphenol A, paraalphacumylphenol Etc.), ketones (eg benzoylacetone, diacetobenzene, benzophenone, tricho Non, heptacosanone, heptatriacontanone, hentriacontanone, heptatriacontanone, stearone, laurone, dianisole, etc.), amides (eg oleic acid amide, lauric acid amide, stearic acid amide, ricinoleic acid amide, palmitic acid amide) , Tetrahydrofuranic acid amide, erucic acid amide, myristic acid amide, 12-hydroxystearic acid amide, N-stearyl erucic acid amide, N-oleyl stearic acid amide, N, N'-ethylenebislauric acid amide, N, N'- Ethylene bis stearic acid amide, N, N'-ethylene bis oleic acid amide, N, N'-methylene bis stearic acid amide, N, N'-ethylene bis behenic acid amide, N, N'-xylylene bis stearic acid amide , N, N'-Buchi Lenbis stearic acid amide, N, N′-dioleyl adipic acid amide, N, N′-distearyl adipic acid amide, N, N′-dioleyl sebacic acid amide, N, N′-cysteallyl sebacic acid amide, Like N, N'-distearyl terephthalamide, N, N'-distearylisophthalamide, phenacetin, toluamide, acetamide, oleic acid dimer / ethylenediamine / stearic acid (1: 2: 2 molar ratio) A reaction product of dimer acid, diamine and fatty acid such as tetraamide), sulfonamide (eg, paratoluenesulfonamide, ethylbenzenesulfonamide, butylbenzenesulfonamide, etc.), silicones (eg, silicone SH6018 (Toray Silicone), Silicone KR215, 216, 220 (Shin-Etsu Corn), etc.), coumarones (for example, Escron G-90 (Nippon Chemical Co., Ltd.), etc.), cholesterol fatty acid esters (for example, stearic acid cholesterol, palmitic acid cholesterol, myristic acid cholesterol, behenic acid cholesterol, lauric acid cholesterol, melisin) Acid cholesterol, etc.), saccharide fatty acid esters (sucrose stearate, sucrose palmitate, sucrose behenate, saccharose laurate, sucrose melinate, lactose stearate, lactose palmitate, lactose myristate, lactose behenate, lactose laurate, melicine Acid lactose, etc.).

  The phase change temperature in the solid-liquid phase change of the solid (phase change) solvent is preferably 60 ° C to 200 ° C, more preferably 80 to 150 ° C.

  The solid (phase change) solvent as described above can be used by dissolving the colored composition of the present invention as it is in a heated molten solvent, and is also dispersed or dissolved in combination with a resinous dispersant or binder. It can also be used.

  For a specific method for preparing such a phase change solvent, methods described in JP-A Nos. 5-186723 and 7-70490 can be referred to.

  The ink jet recording liquid of the present invention in which the colored composition of the present invention is dissolved or dispersed using an aqueous, oily, or solid (phase change) solvent as described above has a viscosity at the time of flight of 0.40 Pa · s or less. Preferably, it is 0.30 Pa · s or less.

The inkjet recording liquid of the present invention preferably has a surface tension of 2 × 10 ⁻⁴ N / cm to 10 ⁻³ N / cm when flying, and preferably 3 × 10 ⁻⁴ N / cm to 8 × 10 ^−4. More preferably, it is N / cm.

  The colored composition of the present invention is preferably used in the range of 0.1 to 25% by mass of the ink jet recording liquid, and more preferably in the range of 0.5 to 10% by mass.

  The resin-type dispersant used in the present invention is preferably a polymer compound having a molecular weight of 1,000 to 1,000,000. When these are used, 0.1 to 50% by mass in the ink jet recording liquid is used. It is preferable to contain.

  The inkjet recording liquid of the present invention includes a viscosity modifier, a surface tension adjuster, a ratio according to the purpose of improving ejection stability, compatibility with print heads and ink cartridges, storage stability, image storage stability, and other various performances. Resistance adjusting agents, film forming agents, dispersants, surfactants, ultraviolet absorbers, antioxidants, fading inhibitors, antifungal agents, rust inhibitors, and the like can also be added.

  The ink jet recording liquid of the present invention is not particularly limited with respect to the recording method to be used, but can be preferably used as an ink jet recording liquid for an on-demand type ink jet printer. As an on-demand type, an electro-mechanical conversion type (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a shared wall type, etc.), an electro-thermal conversion type (for example, a thermal type) Specific examples include an ink jet type, a bubble jet (registered trademark) type, an electrostatic suction type (for example, an electric field control type, a slit jet type, etc.), and a discharge type (for example, a spark jet type). it can.

  The color toner of the present invention is characterized by containing the coloring composition according to the present invention. The content of the coloring composition according to the present invention is preferably 2 to 30% by mass in the toner particles.

  In addition to the colored composition according to the present invention, the color toner is mainly composed of a binder resin, a release agent, a charge control agent, and an external additive.

  As the binder resin for forming the base, all binders generally used for toners can be used. For example, a styrene resin, an acrylic resin, a styrene / acrylic resin, a polyester resin, and the like can be given. In addition, for the purpose of imparting toner fluidity improvement or charging control, external additives such as inorganic fine powder and organic fine particles may be added to the toner. As the external additive, silica fine particles and titania fine particles whose surfaces are treated with an alkyl group-containing coupling agent or the like are preferably used. The number average primary particle diameter of these is preferably 10 to 500 nm, and the addition amount thereof is preferably 0.1 to 20% by mass with respect to the toner.

  Further, as a release agent added to the toner particles for the purpose of improving the heat fixing property, a release agent conventionally used for toner can be used. Specific examples include olefins such as low molecular weight polypropylene, low molecular weight polyethylene, ethylene-propylene copolymer, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax. These addition amounts are preferably 1 to 5% by mass in the toner.

  In addition, the charge control agent for improving the charging characteristics may be added as necessary, but is preferably colorless from the viewpoint of color developability, for example, having a quaternary ammonium salt structure or having a calixarene structure. Etc.

  When the color toner of the present invention is used for a two-component developer, it is used by mixing with a carrier. As the carrier, either an uncoated carrier composed only of magnetic material particles such as iron and ferrite, or a resin-coated carrier whose magnetic material particle surface is coated with a resin or the like may be used. The average particle size of the carrier is preferably 30 to 150 μm in terms of volume average particle size.

  The image forming method to which the color toner of the present invention is applied is not particularly limited. For example, a method of forming an image by repeatedly forming a color image on a photoconductor and then transferring it, or forming on a photoconductor Examples include a method of sequentially transferring the formed image to an intermediate transfer member or the like, forming a color image on the intermediate transfer member or the like, and then transferring the image to an image forming member such as paper to form a color image.

  When the colored composition of the present invention is used for color filters, when dispersing the colored composition of the present invention in a transparent resin, various dispersing means such as a two-roll mill, a three-roll mill, a sand mill, and a kneader can be used.

  In the present invention, as the resin varnish, a varnish used in a conventionally known color filter coloring composition is used. As the dispersion medium, a solvent suitable for the resin varnish or an aqueous medium is used. Further, conventionally known additives such as a dispersion aid, a smoothing agent and an adhesion agent are added and used as necessary.

  As the resin varnish, a photosensitive resin varnish and a non-photosensitive resin varnish are used. Examples of the photosensitive resin varnish are photosensitive resin varnishes used for ultraviolet curable inks, electron beam curable inks, etc., and non-photosensitive resin varnishes include, for example, relief printing inks, planographic inks, intaglio gravure inks, Any of varnishes used for printing inks such as stencil screen inks, varnishes used for electrodeposition coating, varnishes used for developers of electronic printing and electrostatic printing, varnishes used for thermal transfer ribbons, and the like can be used.

  Examples of the photosensitive resin varnish include a photosensitive cyclized rubber resin, a photosensitive phenol resin, a photosensitive polymethacrylate resin, a photosensitive polyamide resin, a photosensitive polyimide resin, and an unsaturated polyester resin. Examples of the varnish include a polyester acrylate resin, a polyepoxy acrylate resin, a polyurethane acrylate resin, a polyether acrylate resin, and a polyol acrylate resin, and a varnish to which a monomer is added as a reactive diluent. The photosensitive coloring composition of the present invention can be obtained by adding a photopolymerization initiator such as benzoin ether or benzophenone to the coloring composition of the present invention and the above varnish, and carrying out brickwork by a conventionally known method. Moreover, it can replace with said photoinitiator and can use it as a thermopolymerizable coloring composition using a thermal polymerization initiator. When forming a color filter pattern using the above photosensitive coloring composition, spin coating the photosensitive coloring composition on a transparent substrate, coating the entire surface using a low-speed rotary coater, roll coater, knife coater, etc. Or performing full printing by various printing methods or partial printing that is slightly larger than the pattern, and after pre-drying, the photomask is brought into close contact, and exposure is performed using an ultrahigh pressure mercury lamp to print the pattern. Next, development and washing are carried out, and post-baking is carried out as necessary to form a color filter pattern.

  Examples of non-photosensitive resin varnishes include cellulose acetate resins, nitrocellulose resins, styrene (co) polymers, polyvinyl butyral resins, amino alkyd resins, polyester resins, amino resin modified polyester resins Resin, polyurethane resin, acrylic polyol urethane resin, soluble polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, casein, hydroxyethyl cellulose, styrene-maleic acid ester copolymer water-soluble Water-soluble salts of (meth) acrylic acid ester (co) polymers, water-soluble amino alkyd resins, water-soluble amino polyester resins, water-soluble polyamide resins, etc., used alone or in combination Is done.

  When forming a color filter pattern using the above-mentioned non-photosensitive coloring composition, the non-photosensitive coloring composition, for example, the above-described various printing methods using a printing ink for color filters is used on a transparent substrate. A method of printing a colored pattern directly on a substrate, a method of forming a colored pattern on a substrate by electrodeposition coating using an aqueous electrodeposition coating composition for color filters, an electronic printing method or an electrostatic printing method, or Examples thereof include a method in which a colored pattern is once formed on a transferable substrate by the above-described method and then transferred to a color filter substrate. Then, according to a conventional method, baking is performed as necessary, polishing for smoothing the surface, or top coating for protecting the surface is performed. Further, a black matrix is formed according to a conventional method to obtain an RGB color filter.

  Hereinafter, a specific example will be described. In the text, “part” or “%” is based on mass unless otherwise specified.

Example 1
Although the manufacturing method of the metal chelate pigment | dye which uses the pigment | dye represented by the said general formula (I) or (III) as a ligand below is shown, this invention is not limited to this.

  Synthesis of exemplary metal chelate dye D-6

  2 g of the exemplified dye 66 was dissolved in 50 ml of methanol, 3.3 g of the exemplified metal ion-containing compound VI-47 was added thereto, and the mixture was reacted for 1 hour while heating under reflux. After completion of the reaction, the solvent was distilled off, and acetonitrile was added for crystallization. The obtained crystals were filtered, washed and dried to obtain the target exemplified metal chelate dye D-6.

  Similarly, the metal chelate dyes D-1 to D-5 and D-7 to D-30 described above were synthesized. Spectral absorption spectra of the obtained metal chelate dyes in an acetone solution were measured, and the maximum molar extinction coefficient of each dye (determined per molecule of dye constituting the metal chelate dye) was measured. Moreover, the following hue evaluation was performed visually. Hereinafter, as representative metal chelate dyes, D-2, 6, 10, 13, 19 and, for comparison, the results of comparative metal chelate dye 1 and comparative dye 3 described below are also shown in Table 2 below. Shown in

Evaluation of hue Hue was evaluated visually as magenta.

○: Hue is the best Δ: Hue is good ×: Hue is poor.

  As shown in Table 2, although the comparative chelate dye 1 and the comparative dye 3 have a higher maximum molar extinction coefficient than the chelate dye of the present invention, the hue is inferior to the chelate dye of the present invention. On the other hand, the metal chelate dye of the present invention has a particularly excellent hue as a magenta dye. Accordingly, a dye image having a very excellent hue can be obtained by using the metal chelate dye of the present invention, and a coloring composition having a very excellent hue can be obtained by containing the metal chelate dye of the present invention. Can be provided.

Example 2
0.2 g of the exemplary metal chelate dye D-6 obtained in Example 1 above, 2.0 g of tricresyl phosphate, and 0.16 g of sodium dodecylbenzenesulfonate were dissolved in 1.3 g of ethyl acetate. Next, 6.8 g of a 15% aqueous solution of lime-processed gelatin and 5.5 g of water were added to a homogeneous mixture at 40 ° C., and the mixture was emulsified and dispersed at 40 ° C. and 10,000 rpm for 10 minutes using a homogenizer. A colored composition was prepared as an emulsified dispersion. In the obtained coloring composition, it added water so that the density | concentration of exemplary metal chelate pigment | dye D-3 might be 0.25 mmol / m < ² >, and this was apply | coated using the wire bar on the support body for photographic paper. The film formed after coating exhibited a good magenta color. Moreover, light resistance was also favorable.

Example 3
(Preparation of fine particle dispersion)
Table 3 shows the dye 5 g, 5 g of polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd. BL-S, average polymerization degree 350) and 50g of ethyl acetate to put in a separable flask, after the inside of the flask N ₂ substitutions, the polymer was stirred And the dye was completely dissolved. After dropping 100 g of an aqueous solution containing 2 g of sodium lauryl sulfate, the mixture was emulsified for 300 seconds using an ultrasonic disperser (UH-150 type, manufactured by SMT Co., Ltd.). Thereafter, ethyl acetate was removed under reduced pressure to obtain colored fine particles impregnated with the dyes shown in Table 3. 0.15 g of potassium persulfate was added to this dispersion and dissolved, and after heating to 70 ° C. with a heater, 7 g of a mixture of 2 g of styrene and 1 g of 2-hydroxyethyl methacrylate was added dropwise. By reacting, a core-shell type colored fine particle dispersion was obtained.

(Preparation of water-based ink)
The above-mentioned colored fine particle dispersion in which the pigment content is 2% by mass with respect to the finished amount of the ink is weighed, ethylene glycol 15% by mass, glycerin 15% by mass, triethylene glycol monobutyl ether 3% by mass, Surfynol. 465 was prepared and mixed so that 0.3% by mass and the remainder was pure water, and further filtered through a 2 μm membrane filter to remove dust and coarse particles. As shown in Table 3, inkjet inks 1 to 7 were used. Got.

(Sample preparation and evaluation)
Furthermore, each ink was printed on Konica photo jet paper Photolique QP glossy paper (made by Konica Minolta IJ Co., Ltd.) using a commercially available Epson inkjet printer (PM-800), and the light resistance of the obtained image was evaluated. The results obtained are also shown in Table 3.

(Light resistance)
Decrease rate of reflection spectral density at the maximum absorption wavelength in the visible region from an unexploded sample after 48 hours of xenon light (70000 lux) bombardment using a xenon weather meter manufactured by Suga Test Instruments Co., Ltd. ), Light resistance (%) = (exposed sample maximum absorption wavelength concentration / unexposed sample maximum absorption wavelength concentration) × 100 was calculated and evaluated as follows. In each case, the light resistance was 90% or more, light resistance A, 80% or more and less than 90% light resistance B, and less than 80% light resistance C.

(Ink storage stability)
The change rate of the particle diameter when each ink was stored at 60 ° C. for 7 days and the filterability of the ink after storage were evaluated. In addition, this particle diameter is an average particle diameter, and was measured by Malvern Co., Ltd. Zetasizer 1000HS.

  Change rate of particle size: Ink was stored at 60 ° C. for 7 days, when the change rate of particle size was less than 5%, ◎ 5% to less than 10% ○ (acceptable level), 10% or more × (Impossible level).

  Filterability: After storing the ink at 60 ° C. for 7 days, 5 ml of the ink was collected and filtered through a 0.8 μm cellulose acetate membrane filter. ), And those that could not be filtered by more than half were marked as x (impossible level).

  As is apparent from the above results, it can be seen that the ink of the present invention is superior in light resistance and ink storage stability as compared with the comparison.

Example 4
<Manufacture of color toner: grinding method>
100 parts by mass of a polyester resin, 8 parts by mass of a dye (colorant) described in Table 4 and 3 parts by mass of polypropylene were mixed, kneaded, pulverized and classified to obtain a powder having a volume average particle size of 8.5 μm. Further, 100 parts by mass of this powder and 1.0 part by mass of silica fine particles (number average primary particle size 12 nm) were mixed with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) to obtain color toners 1 to 5 by a pulverization method.

<Manufacture of color toner: polymerization method>
In an aqueous solution in which 5 g of sodium dodecyl sulfate is dissolved in 200 ml of pure water, 20 g of the coloring matter (coloring agent) shown in Table 4 is added, and stirring and ultrasonic waves are applied, whereby an aqueous dispersion of the coloring agent and a low molecular weight are obtained. An emulsion dispersion in which polypropylene (number average molecular weight = 3200) was emulsified in water so as to have a solid content concentration of 30% by mass with a surfactant while heating was prepared in advance.

  60 g of low molecular weight polypropylene emulsified dispersion is mixed with the above dispersion of the colorant, 220 g of styrene monomer, 40 g of n-butyl acrylate monomer, 12 g of methacrylic acid monomer, 5.4 g of t-dodecyl mercaptan as a chain transfer agent After adding 2000 ml of pure water, emulsion polymerization was carried out by maintaining at 70 ° C. for 3 hours while stirring under a nitrogen stream.

  To 1000 ml of the resulting dispersion of the colorant-containing resin fine particles, sodium hydroxide was added to adjust the pH to 7.0, 270 ml of a 2.7 mol% aqueous potassium chloride solution was added, 160 ml of isopropyl alcohol, and 9.0 g of polyoxyethylene octylphenyl ether having an average degree of polymerization of ethylene oxide of 10 was dissolved in 67 ml of pure water and added, and the reaction was carried out with stirring at 75 ° C. for 6 hours.

  The obtained reaction solution is filtered, washed with water, further dried and pulverized to obtain colored particles, and 1.0 part by mass of the colored particles and silica fine particles (number average primary particle size 12 nm) are combined with a Henschel mixer (Mitsui Miike Chemical Industries). And color toners 6 to 10 were obtained by polymerization.

<Manufacture of developer>
To 10 parts by mass of these color toners, 900 parts by mass of carrier iron powder “EFV250 / 400” (manufactured by Nippon Iron Powder) was uniformly mixed to obtain “developer”.

<Evaluation equipment>
The color toner and developer were set in the developing unit of a commercially available color image forming apparatus “Konica 9331” (manufactured by Konica Minolta Business Technologies Co., Ltd.) adopting an electrophotographic method, printed, and the following evaluation items were evaluated. . In order to clarify the difference in color toner performance, the evaluation was made by modifying the color toner so that it can be used in all four color developing units. The evaluation sample produced the reflection image (image on paper) and the transmission image (OHP image) on paper and OHP, respectively. The color toner was prepared in an amount of 0.65 to 0.75 mg / cm ² . About each obtained image sample, the hue, light fastness, and transparency of an OHP image were evaluated as follows.

《Hue》
The hue was visually evaluated as magenta.

○: Best hue and particularly suitable for use as a color toner Δ: Good hue and suitable for use as a color toner ×: Poor hue and practical problems for use as a color toner

《Light resistance》
The light resistance was evaluated based on the residual dye ratio determined from the difference in image density before and after the xenon light irradiation. For the dye residual ratio, after measuring the color toner image density Ci immediately after image formation, a weather meter “Atlas C.165” (manufactured by Atlas) was used to apply 5 xenon light (85,000 lux) to the color toner image. After irradiation for a day, the color toner image density Cf was measured again, and the residual dye ratio ({(Ci−Cf) / Ci} × 100%) was calculated from the difference in image density before and after the xenon light irradiation. The image density was measured using a reflection densitometer “X-rite 310TR” (manufactured by X-rite Company).

○: Dye remaining ratio is 90% or more and excellent in light resistance. Δ: Dye remaining ratio is 90 to 80%, light resistance is good, and there is no practical problem. ×: Dye remaining ratio is less than 80% and light resistance is improved. Inferior practical problem.

<Transparency of OHP image>
The transparency of the OHP image was evaluated based on the spectral transmittance of each of the following wavelengths. Spectral transmittance was determined by measuring the visible spectral transmittance of a color toner image using a “330-type self-recording spectrophotometer” (manufactured by Hitachi, Ltd.), using an OHP sheet that does not carry color toner as a reference, and measuring at 570 nm. Spectral transmittance was determined.

○: Spectral transmittance is 80% or more and transparency is very good and good Δ: Spectral transmittance is 70 to 80% and transparency is good and no practical problem ×: Spectral transmittance is 70% or less and transparency is poor Practical problem.

  Table 4 shows the evaluation results of hue, light fastness, and transparency of the OHP image.

  As is apparent from Table 4, the image produced using the color toner of the present invention exhibits particularly good hue and high OHP quality, and the color toner of the present invention is suitable for use as a full-color magenta toner. . Furthermore, since an image produced using the color toner of the present invention has good light resistance, it can be stored for a long period of time.

Example 5
<Preparation of photosensitive coating agent for color filter>
In order to obtain an RGB color filter, a mosaic pattern was formed on the glass plate by the following method. A photosensitive coating agent for a color filter was prepared using the components shown below. The used photosensitive polyimide resin varnish is a photosensitive polyimide resin varnish containing a photosensitizer.

<Photosensitive coating component for color filter>
<CF-1>
Illustrative metal chelate dye D-12 10 parts Photosensitive polyimide resin varnish 50 parts N-methyl-2-pyrrolidone 40 parts A glass plate treated with a silane coupling agent is set on a spin coater, and the above CF-1 color filter The photosensitive coating agent was spin-coated at 300 rpm for 5 seconds and then at 2000 rpm for 5 seconds. Next, prebaking was performed at 80 ° C. for 15 minutes, a photomask having a mosaic pattern was brought into close contact, and exposure was performed using an ultrahigh pressure mercury lamp at a light amount of 900 mJ / cm ² . Next, development and washing were performed with a dedicated developer and a dedicated rinse to form a magenta mosaic pattern on the glass plate.

  The color filter obtained above has excellent spectral absorption characteristics, excellent fastness such as light resistance and heat resistance, and also has excellent properties of light transmission, as a color filter for liquid crystal color display It had excellent properties.

Claims (5)

It contains at least one kind of metal chelate dye formed from a dye represented by the following general formula (I) and a metal ion-containing compound comprising a compound represented by the following general formula (V) and a metal ion. Coloring composition.

(In the formula, R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom or a substituent. A ₁ , A ₂ , A ₃ and A ₄ each independently represents C—R ₁₅ or a nitrogen atom; ₁₅ represents a hydrogen atom or a substituent, and when a plurality of R ₁₅ are present, each R ₁₅ may be the same or different, J represents an alkylene group, and R ₄ represents an amino group. Or represents an imino group.)

(In the formula, R ₁₂ represents a substituent. R ₁₃ represents an alkyl group having 2 or more carbon atoms, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, or a heterocyclic group. R ₁₆ represents hydrogen. Represents an atom, a methyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a pivaloylamino group, a cyano group or a chloro group , wherein l represents an integer of 1 to 5, and when l is plural, each R ₁₆ is the same However, they may be different. X represents O, S, SO or SO _2. ) The colored composition according to claim 1, wherein the general formula (I) is represented by the following general formula (III).

(In the formula, R ₁ , R ₂ , R ₃ , A ₁ , A ₂ , A ₃ and A ₄ represent a group having the same meaning as in formula (I). R ₈ , R ₉ , R ₁₀ and R ₁₁ are each Independently represents a hydrogen atom or an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ₁₀ and R ₁₁ may be linked to each other to form a ring.) A color toner comprising at least one coloring composition according to claim 1 or 2. An ink jet recording liquid comprising at least one coloring composition according to claim 1 or 2. An ink jet recording method comprising spraying the ink jet recording liquid according to claim 4 on a recording medium for recording.