JP5130630B2 - Coloring composition, ink jet recording liquid, ink jet recording method, color toner, color filter, and metal chelate dye - Google Patents

Description

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

  Conventionally, as a method for obtaining a color hard copy, a color image recording technique has been studied by inkjet, electrophotography, silver halide photosensitive material, and the like. Color filters are used in electronic parts such as LCDs and PDPs for displays and CCDs for photographic 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 equipment used is low noise and good operability, but also the advantage that it can be easily colored and can use plain paper as a recording member, so it has been widely used in inkjet printers in recent years. 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 is required that the image is fixed fast on the medium and does not bleed after recording, has excellent storability as ink, has no safety problems such as toxicity and flammability, and is inexpensive. From such a viewpoint, 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 yellow ink using a water-soluble dye, C.I. I. Direct Yellow 86 and C.I. I. Although those using azo-based water-soluble dyes such as Direct Yellow 132 are known, since these are short wavelengths, the print density is difficult to increase, and although it is higher than magenta, it has light resistance such as Still has problems with robustness.

  In addition, as a method of improving the light resistance of dyes, a method of coordinating metals to dyes is generally known, and this method is used for the production of ink jet dyes, and it is proposed to contain dyes and metals in the same ink. (For example, refer to 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. Further, an ink jet recording liquid containing an aqueous dispersion of polymer particles containing a metal coordinated to a dye has been proposed (for example, see Patent Documents 2 and 3). There was a drawback.

  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, methine dyes, azo dyes, and water-based ink compositions thereof have been shown for yellow inks for the purpose of achieving both hue and light resistance (see, for example, Patent Document 4). The level of hue and light resistance was not sufficient and further improvements were desired.

  In the case of using a colorant as 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. In addition, the charging performance may change due to separation from the surface of the colorant, and the surface of the fixing roller may be 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 colorant have been disclosed (for example, see Patent Documents 5 to 7). 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 8 to 11). Although improvements have been seen in terms of transparency and hue, it is still insufficient, and light resistance is a pigment. There was a problem that it deteriorated significantly as 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, washing the unexposed portion in a development process, and removing the remaining pattern portion of the filter color. A color filter can be produced by sequentially repeating the operation of dyeing with a dye for all filter colors (see, for example, Patent Document 12). This method uses dyes and has high transmittance, and the optical characteristics of the color filter are excellent, but there is a limit to light resistance, heat resistance, etc., and various colorants with excellent resistance and high transparency are desired. It was rare. Therefore, organic pigments having excellent light resistance and heat resistance have been used in place 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 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 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, an inkjet recording liquid containing the novel metal chelate dye, An inkjet recording method, a color toner, and a color filter are provided.

  The above object of the present invention has been achieved by the following constitution.

  1. A coloring composition comprising at least one metal chelate dye having a dye represented by the following general formula (1) as a ligand.

(In the formula, R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or a phenyl group, R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent. Z ₁ represents —O—, — S—, —N (R ₅ ) — or —C (R ₆ ) (R ₇ ) —, Z ₂ represents —C (R ₈ ) ═ or —C (R ₉ ) (R ₁₀ ) —, Z ₃ represents —C (R ₁₁ ) ═ or —C (R ₁₂ ) (R ₁₃ ) —, and R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ represents a hydrogen atom or a substituent, and the bond between Z ₂ and Z ₃ is a single bond or a double bond, and when R ₈ and R ₁₁ represent a substituent, they may be bonded to each other to form a ring. Z ₄ represents —N═ or —C (R ₁₄ ) ═, Z ₅ represents —N═ or —C (R ₁₅ ) ═, and Z ₆ represents —N═ or —C (R ₁₆ ) ═. R ₁₄ , R ₁₅ and R ₁₆ are hydrogen atoms Represents an alkyl group, an alkenyl group, a cycloalkyl group or a phenyl group, and when R ₁₄ and R ₁₅ represent an alkenyl group, they may be bonded to each other to form a ring.
2. 2. The coloring composition as described in 1 above, wherein the dye represented by the general formula (1) is represented by the following general formula (2).

(Wherein R ₁ and R ₄ represent a hydrogen atom or an alkyl group. Z ₄ represents —N═ or —C (R ₁₄ ) ═, and Z ₅ represents —N═ or —C (R ₁₅ ) ═. Z ₆ represents —N═ or —C (R ₁₆ ) ═, R ₁₄ , R ₁₅ and R _{16 each} represents a hydrogen atom, an alkyl group or a phenyl group, and Z ₁ , Z ₂ and Z ₃ are (It is synonymous with Z ₁ , Z ₂ and Z ₃ in the general formula (1).)
3. 2. The coloring composition as described in 1 above, wherein the coloring matter represented by the general formula (1) is represented by the following general formula (3).

(Wherein, R ₁ and R ₄ represents an alkyl group, R ₁₅ is Z ₁ in the general formula each .Z _1, Z ₂ and Z ₃ represents an alkyl group or a phenyl group (1), Z ₂ and Z Synonymous with _3. )
4). An ink jet recording liquid comprising at least one metal chelate dye having a ligand represented by the dye represented by the general formula (1), (2) or (3) described in 1 to 3 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.

  6). A color toner comprising at least one metal chelate dye having a ligand represented by the dye represented by the general formula (1), (2) or (3) described in 1 to 3 above.

  7). A color filter comprising at least one metal chelate dye having the dye represented by the general formula (1), (2) or (3) described in 1 to 3 as a ligand.

  8). 4. A metal chelate dye having the dye represented by formula (3) described in 3 as a ligand.

  INDUSTRIAL APPLICABILITY According to the present invention, a novel metal chelate dye and a novel coloring composition containing the metal chelate dye can be provided, and an ink jet recording liquid and an ink jet recording method having improved performance by using the novel metal chelate dye Color toners and color filters could be provided.

  Hereinafter, although the best mode for carrying out the present invention will be described, the present invention is not limited to these.

  First, the pigment | dye represented by the said General formula (1) based on this invention is explained in full detail.

In the general formula (1), R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or a phenyl group. Examples of the alkyl group represented by R ₁ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, and neopentyl. Group, 1-ethylpentyl group, n-octyl group, n-nonyl group, n-undecyl group and the like. Examples of the alkenyl group include a vinyl group, 2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group, and cyclohexenyl group. Etc. Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and the like.

When R ₁ represents an alkyl group, an alkenyl group, a cycloalkyl group or a phenyl group, each may have a substituent, and the substituent is not particularly limited. For example, an alkyl group (for example, a methyl group, Ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, trifluoromethyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group etc.), aryl group ( For example, phenyl group, naphthyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, etc.), alkylthio group (eg, methylthio group, ethylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.) Alkenyl group (for example, vinyl group, 2-propenyl group, 3-butenyl group) Group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group, cyclohexenyl group, etc.), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) ), Alkynyl group (eg, propargyl group, etc.), heterocyclic group (eg, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, etc.), alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, etc.), arylsulfonyl Group (eg, phenylsulfonyl group, naphthylsulfonyl group, etc.), alkylsulfinyl group (eg, methylsulfinyl group, etc.), arylsulfinyl group (eg, phenylsulfinyl group, etc.), phosphono group, acyl group (eg, acetyl group, pivaloyl) Group, benzoyl group, etc.), carbamoyl group (eg For example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, butylaminocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylamino) Sulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group) , Sulfonamide groups (for example, methanesulfonamide groups, benzenesulfonamide groups, etc.), cyano groups, alkoxy groups (for example, methoxy groups, etho Si group, propoxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), heterocyclic oxy group, siloxy group, acyloxy group (eg acetyloxy group, benzoyloxy group etc.), sulfonic acid group, Salt of sulfonic acid, aminocarbonyloxy group, amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, etc.), anilino group (for example, , Phenylamino group, chlorophenylamino group, toluidino group, anisidino group, naphthylamino group, 2-pyridylamino group, etc.), imide group, ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, Octylureido group, dodecylu Id group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), alkoxycarbonylamino group (eg methoxycarbonylamino group, phenoxycarbonylamino group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl) Groups, phenoxycarbonyl, etc.), aryloxycarbonyl groups (eg, phenoxycarbonyl group, etc.), heterocyclic thio groups, thioureido groups, carboxyl groups, carboxylic acid salts, hydroxy groups, mercapto groups, nitro groups, and the like. It is done. These substituents may be further substituted with the same substituent.

In the general formula (1), R ₁ is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group, and particularly preferably a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group.

In the general formula (1), R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent. When R ₂ , R _3, and R ₄ represent a substituent, the substituent is not particularly limited, and examples thereof include the same groups as the substituent that the group represented by R ₁ may have. it can. These substituents may be further substituted with the same substituent.

In general formula (1), R ₂ and R ₃ are preferably hydrogen atoms.

In the general formula (1), R ₄ is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group, and a linear alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n- Pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, etc.) are particularly preferred.

In the general formula (1), Z ₁ represents —O—, —S—, —N (R ₅ ) — or —C (R ₆ ) (R ₇ ) —, and Z ₂ represents —C (R ₈ ) = or _{-C (R 9) (R 10} ) - represents, Z ₃ is -C (R ₁₁₎ = or _{-C (R 12) (R 13} ) - _{represents, R 5, R 6, R} 7, R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ represent a hydrogen atom or a substituent. When R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ represent a substituent, the substituent is not particularly limited, but for example, represented by R ₁ The same group as the substituent which the group which may have may be mentioned. These substituents may be further substituted with the same substituent. When R ₈ and R ₁₁ represent a substituent, they may be bonded to each other to form a ring.

In the general formula (1), the bond between Z ₂ and Z ₃ is a single bond or a double bond.

In the general formula (1), Z ₄ represents —N═ or —C (R ₁₄ ) ═, Z ₅ represents —N═ or —C (R ₁₅ ) ═, and Z ₆ represents —N═ or —C. (R ₁₆ ) = is represented, and R ₁₄ , R ₁₅ and R ₁₆ represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or a phenyl group. When R ₁₄ and R ₁₅ represent an alkenyl group, they may be bonded to each other to form a ring. R _14, R ₁₅ and R ₁₆ is an alkyl group, when an alkenyl group, a cycloalkyl group or a phenyl group, each may have a substituent is not particularly limited as substituents, For example, R ₁ The group similar to the substituent which the group represented by may have may be mentioned. These substituents may be further substituted with the same substituent.

In the general formula (1), R ₁₄ , R ₁₅ and R ₁₆ are preferably a hydrogen atom, an alkyl group or a phenyl group, more preferably an alkyl group or a phenyl group, and particularly preferably an alkyl group.

  The dye represented by the general formula (1) according to the present invention may have an isomer structure represented by the following general formulas (1) ′, (1) ″ and (1) ′ ″. In the present invention, it is described in one typical form represented by the general formula (1), but isomers such as the following general formula different from the description of the present invention are also included in the present invention.

  The general formula (1) specifically includes the following general formulas (1-a), (1-b), (1-c), (1-d), (1-e), (1-f). , (1-g), (1-h), (1-i), (1-j), (1-k) or (1-l), of which the general formula ( 1-a), (1-c) and (1-d) are preferred.

_{Wherein, R 1, R 2, R} 3, R 4, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, Z 1, Z 2, Z 3 , Z ₄ , Z ₅ and Z ₆ are R ₁ , R ₂ , R ₃ , R ₄ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R _{14 in the} general formula (1). , R ₁₅ , R ₁₆ , Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ and Z ₆ . R ₁₇ and R ₁₈ represent a substituent, and the substituent is not particularly limited, and examples thereof include the same groups as the substituent that the group represented by R ₁ may have. These substituents may be further substituted with the same substituent. The substituent represented by R ₁₇ and R ₁₈ is preferably an alkyl group or a halogen atom. m represents an integer of 0 to 4, and m is preferably 0 or 1. When m represents an integer of 2 or more, the plurality of R ₁₇ may be the same or different. n represents an integer of 0 to 4, and n is preferably 0 or 1. When n represents an integer of 2 or more, the plurality of R ₁₈ may be the same or different.

  The general formula (1-a) is preferably represented by the following general formula (1-m) or (1-n), and the general formula (1-c) is represented by the following general formula (1-o). Preferably it is done.

In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₁₂ , R ₁₃ , R ₁₇ , m, Z ₄ , Z ₅ and Z ₆ represent the above general formulas (1-a) and (1-c). Are the same as R ₁ , R ₂ , R ₃ , R ₄ , R ₁₂ , R ₁₃ , R ₁₇ , m, Z ₄ , Z ₅ and Z ₆ .

  The general formula (1-d) is preferably represented by the general formula (3).

  Next, the dye represented by the general formula (2) according to the present invention will be described in detail.

In the general formula (2), R ₁ and R ₄ are a hydrogen atom or an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group). , A trifluoromethyl group, etc.) and an alkyl group, it may have a substituent. Z ₄ represents -N = or -C (R ₁₄ ) =, Z ₅ represents -N = or -C (R ₁₅ ) =, and Z ₆ represents -N = or -C (R ₁₆ ) =. , R ₁₄ , R ₁₅ and R ₁₆ are each a hydrogen atom, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, trifluoromethyl) Group) or a phenyl group, and an alkyl group or a phenyl group, it may have a substituent. When R ₁₄ , R ₁₅ and R ₁₆ represent a phenyl group having a substituent, the substituent is preferably an alkyl group or a halogen atom, more preferably an alkyl group, and particularly preferably a methyl group. Z _1, Z ₂ and Z ₃ has the same meaning as Z _1, Z ₂ and Z ₃ in the general formula respectively (1).

In the general formula (2), R ₁ is preferably an alkyl group, more preferably a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group. In the general formula (2), R ₄ is preferably an alkyl group, and a linear alkyl group (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n -Octyl group, n-dodecyl group, etc.) are more preferable. In the general formula (2), R ₁₄ , R ₁₅ and R ₁₆ are preferably an alkyl group or a phenyl group, and particularly preferably an alkyl group.

  Next, the dye represented by the general formula (3) according to the present invention will be described in detail.

In the general formula (3), R ₁ and R ₄ are alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, trifluoro group). Represents a methyl group or the like, and may have a substituent. R ₁₅ represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a trifluoromethyl group, etc.) or a phenyl group. It may have a group. When R ₁₅ represents a phenyl group having a substituent, the substituent is preferably an alkyl group or a halogen atom, more preferably an alkyl group, and particularly preferably a methyl group. Z _1, Z ₂ and Z ₃ has the same meaning as Z _1, Z ₂ and Z ₃ in the general formula respectively (1).

In the general formula (3), R ₁ is preferably a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group. In the general formula (3), R ₄ represents a linear alkyl group (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n -Dodecyl group, etc.) are preferred. In the general formula (3), R ₁₅ is preferably an alkyl group.

  Hereinafter, although the specific example of the pigment | dye represented by the said General formula (1), (2) or (3) is shown, this invention is not limited by the following specific examples.

  Next, the metal chelate dye having the dye represented by the general formula (1), (2) or (3) according to the present invention as a ligand will be described.

  The metal chelate dye having the dye represented by the general formula (1), (2) or (3) as a ligand is preferably represented by the general formula (1), (2) or (3). Obtained by reacting a dye with a divalent metal salt. The method of synthesizing the metal chelate dye can be synthesized according to the method described in “Chelate Chemistry (5) Complex Chemistry Experimental Method [I] (Edited by Nanedo)”. Divalent metal salts used include nickel chloride, nickel acetate, magnesium compounds represented by magnesium chloride, calcium compounds represented by calcium chloride, barium chloride, zinc chloride, zinc acetate, titanium (II) chloride, Examples thereof include iron (II) chloride, copper (II) chloride, cobalt chloride, and manganese (II) chloride. Preferred are nickel chloride, nickel acetate, copper chloride, copper acetate, cobalt chloride, zinc chloride, and zinc acetate. The metal chelate dye used in the present invention may have a neutral ligand depending on the central metal, and typical ligands include water, alcohols and amines.

  Furthermore, you may obtain by making the pigment | dye represented by the said General formula (1), (2) or (3) react with the metal ion containing compound represented by the following.

The metal ion-containing compound is preferably an organic salt of a metal ion or a metal complex. Examples of the metal include monovalent and polyvalent metals belonging to Groups I to VIII of the periodic table. Among them, Al, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Sn, Ti, and Zn are included. Ni, Cu, Cr, Co and Zn are more preferable, Ni and Cu are further preferable, and Ni is particularly preferable. Specific examples of the metal ion-containing compound include Ni ²⁺ , Cu ²⁺ , Cr ²⁺ , Co ²⁺ and Zn ²⁺ and aliphatic salts such as acetic acid and stearic acid, or fragrances such as benzoic acid and salicylic acid. In addition to the salts of group carboxylic acids, the metal ion-containing compound represented by the following general formula (6) can be particularly preferably used.

General formula (6) [X (Q1) _a (Q2) _b (Q3) _c ] ^{P +} (Y ⁻ ) _P
In the general formula (6), X represents a metal ion, preferably Ni ²⁺ , Cu ²⁺ , Cr ²⁺ , Co ²⁺ , Zn ²⁺ , more preferably Ni ²⁺ , Cu ²⁺ , Zn ^2+. And particularly preferably represents Ni ²⁺ . Q1, Q2, and Q3 each represent a coordination compound capable of coordinating with the metal represented by X, and may be the same or different from each other. These coordination compounds can be selected from, for example, coordination compounds described in the above-mentioned chelate science (5) (Nan Edo). Y ^- is represents an organic anion group, and specific examples include tetraphenyl boron anion and alkylbenzene sulfonate anion. a represents an integer of 1, 2 or 3; b represents 1, 2 or 0; c represents 1 or 0; in these, the complex represented by the above general formula is tetradentate or hexadentate It is determined depending on whether it is coordinated or determined based on the number of ligands of Q1, Q2, and Q3. P represents 0, 1 or 2. In P = 0, the coordination compounds represented by Q1, Q2, and Q3 are anionic compounds, and an anionic compound represented by Q1, Q2, and Q3 and a metal ion represented by X (also referred to as a metal cation). ) Is electrically neutralized.

  There is no limitation on the mixing ratio (molar ratio) between the chelatable dye and the metal salt or metal ion-containing compound. When dye: metal ion-containing compound = 1: N, N is preferably 0.01-100. More preferably 0.1 to 10, and still more preferably 0.3 to 5.

  The metal chelate dye is obtained by dissolving a metal salt or metal ion-containing compound powder or an organic solvent in a solution obtained by dissolving or dispersing the dye represented by the general formula (1), (2), or (3) in an organic solvent. It is prepared by adding a solution dissolved in The metal chelate dye may be isolated as a crystal. If isolation is difficult, the solvent may be distilled off and the residue may be used. The residue may be dissolved in another solvent and used. Also good.

  Specific examples of the metal salt and the metal ion-containing compound represented by the general formula (6) are given below, but the invention is not limited to these.

  The metal chelate dye having the dye represented by the general formula (1), (2) or (3) as a ligand is preferably represented by the following general formula (7).

General formula (7) M ^{Q +} (D) _d (L) _Q
In general formula (7), M represents a metal, preferably represents Ni, Cu, Cr, Co, or Zn, more preferably represents Ni, Cu, or Zn, and particularly preferably represents Ni. Q represents an integer of 1 to 3, preferably 2 or 3, and particularly preferably 2. That is, M ^{Q +} represents a metal ion, preferably represents Ni ²⁺ , Cu ²⁺ , Cr ²⁺ , Co ²⁺ , Zn ²⁺ , and more preferably represents Ni ²⁺ , Cu ²⁺ , Zn ²⁺ . Particularly preferably, it represents Ni ²⁺ .

  In General Formula (7), D represents the pigment | dye represented by the said General Formula (1), (2), and (3), d represents the integer of 1-3, and 1 or 2 is preferable. In General Formula (7), L represents an anion (also referred to as an anion).

  Hereinafter, specific examples of the metal chelate dye having the dye represented by the general formula (1), (2) or (3) as a ligand are shown, but the present invention is not limited to the following specific examples. Absent.

  Next, the coloring composition characterized by containing the metal chelate pigment | dye which makes the pigment | dye represented by the said General formula (1), (2) or (3) a ligand is demonstrated.

  The colored composition of the present invention is not particularly limited as long as it is a colored composition containing a metal chelate dye having the dye represented by the general formula (1), (2) or (3) as a ligand. .

  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, the spectral absorption characteristics of the dye may change due to chelation with a metal, and there are merits in color reproduction such as an increase in molar extinction coefficient and sharpening to provide 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 inkjet recording liquid of the present invention contains at least one metal chelate dye having the dye represented by the general formula (1), (2) or (3) as a ligand, and is a metal chelate dye outside the present invention. It may be used in combination.

  The inkjet recording liquid containing a metal chelate dye having the dye represented by the general formula (1), (2) or (3) of the present invention as a ligand is an aqueous solvent, an oil solvent, a solid (phase change). Various solvent systems such as a solvent can be used, and the effects of the present invention are exhibited particularly when an aqueous solvent is used. 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 is used as long as the metal chelate dye having the dye represented by the general formula (1), (2) or (3) of the present invention as a ligand is soluble in the solvent system. It can be used by dissolving.

  On the other hand, when the metal chelate dye having the dye represented by the general formula (1), (2) or (3) of the present invention as a ligand is insoluble in the solvent system as it is, various metal chelate dyes are used. Using a disperser (eg, ball mill, sand mill, attritor, roll mill, agitator mill, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, jet mill, ang mill, etc.) or soluble organic After the metal chelate dye is dissolved in the solvent, it can be dispersed in the solvent system together with the polymer dispersant and the surfactant. Furthermore, in the case of an insoluble liquid or a semi-molten product as it is, it can be dissolved as it is or in a soluble organic solvent and dispersed in the solvent system together with a polymer dispersant or a surfactant.

  When the metal chelate dye having the dye represented by the general formula (1), (2) or (3) of the present invention as a ligand is insoluble in the solvent system, the solvent system is formed into fine particles. It is preferable to be 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 a projected area of a transmission electron microscope (TEM) photograph (obtained for at least 100 particles or more) is converted into a sphere. Is required. The coefficient of variation can be determined 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 the standard deviation thereof can be obtained using a dynamic light scattering method. For example, it can be determined using a laser particle size analysis system manufactured by Otsuka Electronics or a Zetasizer manufactured by Malvern.

  In addition, after dissolving the metal chelate dye in an organic solvent in which the metal chelate dye having the dye represented by the general formula (1), (2) or (3) of the present invention as a ligand is soluble, It is preferable to disperse in an aqueous solvent as a fine particle dispersion together with the polymer.

  Specific examples of the method for preparing the aqueous solvent used for such an ink jet recording liquid include, for example, JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515 and 7. Reference can be made to the methods described in the publications of -1185854.

  Next, the oil-soluble polymer will be described. There is no restriction | limiting in particular as an 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. The 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 dissociative group such as carboxylic acid and 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, 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 from the viewpoint of dispersion stability of the colored fine particles.

  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 esters of polyethylene glycol monoalkyl ether and carboxylic acid monomers, esters of polyethylene glycol monoalkyl ether and sulfonic acid monomers, polyethylene glycol monoalkyl ether and phosphoric acid. Examples thereof include an ester with a 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. The repeating number of the ethyleneoxy part of the polyethylene glycol monoalkyl ether is preferably 8 to 50, more preferably 10 to 30. 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, solubility) It can be appropriately selected according to improvement, dispersion stability, etc.

  The oil solvent used in the present invention is an organic solvent.

  Examples of oil-based solvents include alcohols (for example, pentanol, heptanol, octanol, phenylethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, anis alcohol, etc.), esters (for example, 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, lauric acid Butyl, isopropyl myristate, triethyl phosphate, tributyl phosphate, diethyl phthalate, dibutyl phthalate, diethyl malonate, malo Dipropyl acid, diethyl diethyl malonate, diethyl succinate, dibutyl succinate, diethyl glutarate, diethyl adipate, dipropyl adipate, dibutyl adipate, di (2-methoxyethyl) adipate, diethyl sebacate, diethyl maleate, Dibutyl maleate, 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 ketone, benzylacetone, diacetone alcohol, cyclohexanone, etc.), hydrocarbons (eg petroleum ether, petroleum benzyl, tetralin, decalin, tertiary amylbenzene, dimethylnaphthalene), amide (E.g., N, N-diethyldodecanamide, etc.).

  The oil-based solvent as described above can be used by dissolving the metal chelate dye having the dye represented by the general formula (1), (2) or (3) of the present invention as a ligand as it is, Moreover, it 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, 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 amide, lauric amide, stearic amide, ricinoleic amide, palmitic 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.)), 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 (for example, sucrose stearate, sucrose palmitate, saccharose behenate, saccharose laurate, saccharose melicinate, lactose stearate, lactose palmitate, lactose myristate, lactose behenate, lactose laurate) , Lactose melicinate, etc.).

  The phase change temperature in the solid-liquid phase change of the solid (phase change) solvent is preferably 60 to 200 ° C, and more preferably 80 to 150 ° C. The solid (phase change) solvent as described above is a metal chelate dye having a dye represented by the general formula (1), (2) or (3) of the present invention as a ligand in a heated molten solvent. Can be dissolved and used as it is, and can also be used by dispersing or dissolving in combination with a resinous dispersant or binder.

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

  Metal chelate dyes using the water-based, oil-based, solid (phase change) solvents as described above and having the dye represented by the general formula (1), (2) or (3) of the present invention as a ligand. In the ink jet recording liquid of the present invention in which is dissolved or dispersed, the viscosity at the time of flight is preferably 40 cP or less, and more preferably 30 cP or less.

The ink jet recording liquid of the present invention preferably has a surface tension during flight of 2 × 10 ⁻⁴ to 10 ⁻³ N / cm, more preferably 3 × 10 ⁻⁴ to 8 × 10 ⁻⁴ N / cm. preferable.

  The metal chelate dye having the dye represented by the general formula (1), (2) or (3) of the present invention as a ligand is used in the range of 0.1 to 25% by mass of the ink jet recording liquid. Is preferable, and the range of 0.5 to 10% by mass is more preferable.

  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 has a viscosity adjusting agent, a surface tension adjusting agent, a specific resistance depending on the purpose of improving ejection stability, compatibility with a print head and ink cartridge, storage stability, image storage stability, and other various performances. An adjuster, a film-forming agent, a dispersant, a surfactant, an ultraviolet absorber, an antioxidant, a fading inhibitor, an antifungal agent, a rust inhibitor, 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 a metal chelate dye having the dye represented by the general formula (1), (2) or (3) of the present invention as a ligand. The content of the metal chelate dye having the dye represented by the general formula (1), (2) or (3) of the present invention as a ligand is preferably 2 to 30% by mass in the toner particles. . The color toner mainly includes a binder resin, a release agent, and a charge control agent in addition to the metal chelate dye having the dye represented by the general formula (1), (2) or (3) of the present invention as a ligand. , Composed of external additives.

  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. Further, external additives such as inorganic fine powder and organic fine particles may be added to the toner for the purpose of improving the fluidity of the toner and controlling charging. 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.

  In addition, as a release agent added to the toner particles for the purpose of improving the heat fixing property, a release agent conventionally used for toners 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 development, for example, having a quaternary ammonium salt structure or a calixarene structure. And the like.

  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 to form an image, or a photoconductor Examples include a method in which the formed image is sequentially transferred to an intermediate transfer member or the like, a color image is formed on the intermediate transfer member or the like, and then transferred to an image forming member such as paper to form a color image.

  When the metal chelate dye having the dye represented by the general formula (1), (2) or (3) of the present invention as a ligand is used for a color filter, the metal chelate dye is dispersed 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 colored composition for a color filter is used. As the dispersion medium, a solvent or an aqueous medium suitable for the resin varnish is used. If necessary, conventionally known additives such as a dispersion aid, a smoothing agent, and an adhesive agent are added and used.

  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, and varnishes used for thermal transfer ribbons 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 include varnishes such as polyester acrylate resins, polyepoxy acrylate resins, polyurethane acrylate resins, polyether acrylate resins, polyol acrylate resins, and varnishes to which a monomer is added as a reactive diluent. A photopolymerization initiator such as benzoin ether or benzophenone is added to the metal chelate dye having the dye represented by the general formula (1), (2) or (3) of the present invention as a ligand and the above varnish. It can be set as the photosensitive coloring composition which concerns on this invention by bricking by a well-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 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. Subsequently, development and washing are performed, and post-baking is performed 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 Salts, water-soluble salts of (meth) acrylic acid ester (co) polymers, water-soluble aminoalkyd resins, water-soluble aminopolyester resins, water-soluble polyamide resins, and the like. These can be used alone or in combination. The

  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 a color filter, an electronic printing method or an electrostatic printing method, or a transfer And a method of once forming a colored pattern on the conductive substrate by the above-mentioned method and the like and transferring it to the 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.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to a following example.

Synthesis Example Synthesis of Exemplified Dye 1-48

  7.0 g of Compound A, 18.2 g of Compound B, and 8.0 g of triethylamine were added to 200 ml of acetonitrile and reacted at room temperature for 12 hours. After completion of the reaction, acetonitrile was removed under reduced pressure, and ethyl acetate was added to the resulting residue. The ethyl acetate layer was washed with water, washed with an aqueous sodium hydrogen carbonate solution, washed again with water, and then under reduced pressure. When ethyl acetate was removed, crystals were precipitated. This was recrystallized from isopropanol to obtain 11 g of a yellow solid.

¹ H-NMR and MASS spectrum of the obtained solid were measured to confirm that it was the target Exemplified Dye 1-48. The yield was 84%.

Example 1
Although the preparation method of the metal chelate pigment | dye which uses the pigment | dye represented by the said General formula (3) as a ligand below is shown, this invention is not limited to this.

  Synthesis of exemplary metal chelate dye D-3

  2 g of Exemplified Dye 1-48 was dissolved in 50 ml of methanol, 1.6 g of Exemplified Metal Ion-Containing Compound M-14 was added thereto, and reacted for 1 hour under heating and 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-3.

  Similarly, metal chelate dyes described in Table 1 below 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. The results are also shown below. For comparison, the results of comparative metal chelate dyes 2-1 and 2-2 described below are also shown.

  The hue was visually evaluated as yellow.

○: Hue is the best △: Hue is good ×: Hue is bad

  As Table 1 shows, the metal chelate dye of the present invention has a large maximum molar extinction coefficient and has a particularly excellent hue as a yellow dye. Accordingly, by using the metal chelate dye of the present invention, a dye image having a very excellent hue can be obtained, and by containing the metal chelate dye of the present invention, a coloring composition having a very excellent hue Can be provided.

  (Structure of the comparative metal chelate dye used)

Example 2
0.2 g of the exemplary metal chelate dye D-3 obtained in Example 1, 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 yellow color and good light resistance.

Example 3
(Preparation of water-based ink)
Weighed the dyes listed in Table 2 so that the dye content was 2% by weight as the finished ink, ethylene glycol 15%, glycerin 15%, Surfynol 465 (Nisshin Chemical Industry Co., Ltd.) 0.3%, The remainder was dissolved and prepared so as to be pure water, and further filtered through a 2 μm membrane filter to remove dust and coarse particles to obtain inkjet inks 1 to 8.

(Sample preparation and evaluation)
Furthermore, each ink was printed on Konica photo jet paper Photolike QP glossy paper (made by Konica Minolta Co., Ltd.) using a commercially available Epson inkjet printer (PM-800), and the resulting images were evaluated for light resistance and hue. Table 2 shows the results of the above.

  Light resistance: The rate of decrease in 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.

  Hue: The hue was visually evaluated as yellow.

○: Best hue and particularly suitable for use as an ink jet recording liquid Δ: Good hue and suitable for use as an ink jet recording liquid ×: Poor hue and practical use as an ink jet recording liquid Top problem.

  As is clear from the above results, it can be seen that the present invention is superior in light resistance and hue as compared with the comparison.

  (Structure of comparative dye and comparative metal chelate dye used)

Example 4
(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 11 to 16 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 Co., Ltd.) using a commercially available Epson inkjet printer (PM-800), and the light resistance of the obtained image was evaluated. The results 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.

  (Structure of comparative dye and comparative metal chelate dye used)

Example 5
<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, and 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 a “developer”.

<Evaluation equipment>
The above color toner and developer are 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, printing is performed, and the following evaluation items are evaluated. went. 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 yellow.

○: 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 80 to 89%, 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.) with reference to an OHP sheet on which no color toner is carried, 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 79% and transparency is good and no practical problem ×: Spectral transmittance is less than 70% 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 yellow toner for full color. . 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.

  (Structure of the comparative metal chelate dye used)

Example 6
<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-16 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 yellow 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 (6)

A metal chelate dye having a dye represented by the following general formula (1-a) or (1-c) as a ligand.

(Wherein R ₁ represents an alkyl group which may have a substituent, R ₂ and R ₃ represent a hydrogen atom, and R ₄ represents an alkyl group which may have a substituent. Z ₁ is -O-, or -S - _{represents, R 9, R 10, R} 12 and _{R 13 .R 17} represents a hydrogen atom or a substituent represents a substituent, m is an integer of 0-4. Z ₄ represents -N =, Z ₅ represents -C (R ₁₅ ) =, Z ₆ represents -N =, and R ₁₅ has an alkyl group or a substituent which may have a substituent. The substituent is an alkyl group, cycloalkyl group, aryl group, acylamino group, alkylthio group, arylthio group, alkenyl group, halogen atom, alkynyl group, heterocyclic group, alkylsulfonyl group, aryl. Sulfonyl group, alkylsulfinyl group, aryl Rufinyl group, phosphono group, acyl group, carbamoyl group, sulfamoyl group, sulfonamido group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, sulfonic acid group, sulfonic acid salt, amino Carbonyloxy group, amino group, anilino group, imide group, ureido group, alkoxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic thio group, thioureido group, carboxyl group, carboxylic acid salt, hydroxy group, mercapto Group or nitro group.) A coloring composition comprising at least one metal chelate dye according to claim 1 . An ink jet recording liquid comprising at least one metal chelate dye according to claim 1 . An ink jet recording method comprising: spraying the ink jet recording liquid according to claim 3 on a recording medium for recording. A color toner comprising at least one metal chelate dye according to claim 1 . A color filter comprising at least one metal chelate dye according to claim 1 .