JP2007051123A - Metal-containing compound, metal chelate pigment, coloring composition, ink-jet printing liquid, ink-jet printing method, color toner, color filter, optical information recording medium and optical information recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new metal-containing compound, to provide a metal chelate pigment and a coloring composition obtained from the metal-containing compound, to provide an ink-jet printing liquid containing the metal chelate pigment, to provide an ink-jet printing method using the ink-jet recording liquid, to provide a color toner, a color filter and an optical information recording medium containing the metal chelate pigment, and to provide an optical information recording method using the optical information recording medium. <P>SOLUTION: The metal-containing compound is obtained by reacting a compound represented by general formula (1) with a divalent metal salt. Wherein, R<SB>1</SB>and R<SB>2</SB>are an alkyl or a cycloalkyl; and R<SB>3</SB>is a substituted phenoxy. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a metal-containing compound, a metal chelate dye, an inkjet recording liquid, an inkjet recording method, a color toner, a color filter, an optical information recording medium, and an optical information recording method.

  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, or the like. In addition, color filters are used in electronic parts such as LCDs and PDPs in displays and CCDs in photography equipment. Furthermore, in the field of optical information recording, a dye is used in the recording layer of a write-once disc.

  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 used in an ink jet printer usually uses a water-soluble dye and a polyhydric alcohol in order to prevent the ink from clogging the nozzle. However, this ink has the disadvantage that water-soluble dyes are inferior in water resistance. In order to improve the water resistance of the ink for inkjet recording, a pigment is used for the ink (for example, refer to Patent Document 1), a non-aqueous liquid medium (for example, refer to Patent Document 2), and water resistance is excellent. It is proposed to use a dye (for example, see Patent Document 3). However, these inks have drawbacks such as a decrease in printing density and poor 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 4). However, this method has a drawback in that by coordinating a metal to the dye, the solubility in water is lowered, so that the dye may precipitate and clogging may occur in an inkjet nozzle.

  On the other hand, there has been proposed an ink jet recording liquid containing an aqueous dispersion of polymer particles containing a metal coordinated with a dye (see, for example, Patent Documents 5 and 6). There was a drawback.

  In the case of using a dye 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. 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 colorant are disclosed (for example, see Patent Documents 7 to 9). 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 10 to 12). Although improvements have been seen in transparency and hue, it is still insufficient, and light resistance is a pigment. Compared with the case of using, it has deteriorated significantly.

  In addition, since the color filter is required 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 13). 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. Thus, organic pigments having excellent light resistance and heat resistance have been used instead of dyes, but it has been difficult to obtain optical properties like dyes with color filters using pigments.

  Conventionally, an optical information recording medium (optical disk) capable of recording information only once by laser light is known. This optical disc is also called a write once disc (so-called CD-R), and its typical structure is a recording layer made of an organic dye on a transparent disk-shaped substrate, a light reflecting layer made of a metal such as gold, and a resin. A protective layer made of a metal is provided in this order in a laminated state. Information is recorded on the CD-R by irradiating the CD-R with a near-infrared laser beam (usually a laser beam having a wavelength of about 780 nm), and the irradiated portion of the recording layer is irradiated with the light. The temperature is locally increased by absorbing the water, and a physical or chemical change (for example, generation of pits) is caused to change its optical characteristics, whereby information is recorded. On the other hand, reading (reproduction) of information is also performed by irradiating laser light having the same wavelength as that of the recording laser light, and the portion where the optical characteristics of the recording layer have changed (recorded portion) and the portion not changed (unrecorded) Information is reproduced by detecting the difference in reflectance from (part).

  In recent years, an optical information recording medium having a higher recording density has been demanded. In response to such a demand, an optical disc called a write-once digital versatile disc (so-called DVD-R) has been proposed (see, for example, Non-Patent Document 1). This DVD-R is a transparent disk-shaped substrate in which the guide groove (pre-groove) for tracking the irradiated laser beam is narrower than half of the CD-R (0.74-0.8 μm). On top of this, a recording layer made of a dye, and usually two light reflecting layers on the recording layer, and further a protective layer provided if necessary, or a disk-shaped protective substrate having the same shape as the disk It has a structure in which the recording layer is inside and bonded with an adhesive. Information recording / reproduction to / from DVD-R is performed by irradiating visible laser light (usually laser light having a wavelength in the range of 630 to 680 nm), and higher density recording than CD-R is possible. ing.

  Recently, networks such as the Internet and high-definition TV are rapidly spreading. In addition, broadcasting of HDTV (High Definition Television) has started, and a demand for a large-capacity recording medium is increasing in order to record image information inexpensively and easily. Although the DVD-R is secured to a certain extent as a large-capacity recording medium, it cannot be said that the DVD-R has a large enough recording capacity to meet future requirements. Therefore, development of an optical disc having a higher recording capacity by improving the recording density by using a laser beam having a wavelength shorter than that of the DVD-R is underway.

  Conventionally, in an optical information recording medium having a recording layer containing an organic dye, a recording / reproducing method for recording / reproducing information by irradiating a laser beam having a wavelength of 530 nm or less from the recording layer side toward the light reflecting layer side has been proposed. (For example, see Patent Documents 14 to 28).

Specifically, an optical disk using a porphyrin compound, an azo dye, a metal azo dye, a quinophthalone dye, a trimethine cyanine dye, a dicyanovinylphenyl skeleton dye, a coumarin compound, a naphthalocyanine compound, etc. as a dye of the recording layer, There has been proposed an information recording / reproducing method for recording / reproducing information by irradiating a blue (wavelength 430 nm, 488 nm) or blue-green (wavelength 515 nm) laser beam.
JP-A-4-28776 JP-A-4-261478 US Pat. No. 4,963,189 JP-A-8-156399 JP 2001-18880 A JP 2001-26731 A 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. 5-80213 JP-A-4-74690 JP-A-7-304256 JP-A-7-304257 JP-A-8-127174 Japanese Patent Laid-Open No. 11-53758 JP-A-11-334204 JP 11-334205 A Japanese Patent Laid-Open No. 11-334206 JP 11-334207 A JP 2000-43423 A JP 2000-108513 A JP 2000-113504 A JP 2000-149320 A JP 2000-158818 A JP 2000-228028 A "Nikkei New Media" separate volume "DVD", 1995

  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-containing compound, a metal chelate dye and a coloring composition from the metal-containing compound, and an ink jet recording liquid containing the metal chelate dye It is another object of the present invention to provide an ink jet recording method using the ink jet recording liquid, and a color toner, a color filter, an optical information recording medium containing the metal chelate dye, and an optical information recording method using the optical information recording medium. .

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

  1. A metal-containing compound obtained by reacting a divalent metal salt with a compound represented by the following general formula (1).

(In the formula, R ₁ and R ₂ represent an alkyl group or a cycloalkyl group, and R ₃ represents a group represented by the following general formula (2) or (3)).

(In the formula, R ₄ represents a group represented by —CN or —LR ₁₀ , L represents a divalent linking group containing at least one of an oxygen atom, a sulfur atom or a nitrogen atom, and R ₁₀ represents R ₅ represents a substituent, m represents an integer of 0 to 4, and when m is 2 or more, a plurality of R ₅ may be the same or different. )

(In the formula, R ₆ represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and n represents an integer of 0 to 2.)
2. In the general formula (1), the group represented by R ₃ represents the general formula (2), and the group represented by R ₄ in the general formula (2) is a group represented by —CN. 2. The metal-containing compound as described in 1 above.

3. In the general formula (1), the group represented by R ₃ represents the general formula (2), and the group represented by R ₄ in the general formula (2) is represented by -LR _10. 2. The metal-containing compound as described in 1 above, wherein

4). In the general formula (1), the group represented by R ₃ represents the general formula (2), and the divalent linking group represented by L in the general formula (2) is —O— or —S—. , —CO—, —CO ₂ —, —OCO—, —SO—, —SO ₂ —, —CONR ₁₁ ——NR ₁₂ CO—, —SO ₂ NR ₁₃ —, —NR ₁₄ SO ₂ —, —NR ₁₅ CONR ₁₆ −, —NR ₁₇ CO ₂ —, —OCONR ₁₈ —, —CONR ₁₉ SO ₂ —, —SO ₂ NR ₂₀ CO— (R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , and R ₂₀ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.) The metal-containing compound according to 1 or 3 above .

5. 2. The metal-containing compound as described in 1 above, wherein in the general formula (1), the group represented by R ₃ represents the general formula (3), and n in the general formula (3) is 2. .

6). In the general formula (1), the group represented by R ₃ represents the general formula (3), and the group represented by R ₆ in the general formula (3) is an aryl group. 6. The metal-containing compound according to 1 or 5.

7). 7. The metal-containing compound as described in any one of 1 to 6 above, wherein in the general formula (1), the group represented by R ₁ is a linear alkyl group.

8). 8. The metal-containing compound as described in 7 above, wherein the linear alkyl group represented by R ₁ is a methyl group.

9. In Formula (1), a metal-containing compound according to any one of the 1-8 group represented by R ₂ is equal to or an alkyl group having 11 to 18 carbon atoms.

  10. The metal chelate pigment | dye obtained from at least 1 type of the chelate which can chelate with at least 1 type of the metal containing compound of any one of said 1-9.

  11. 11. A coloring composition comprising at least one of the metal chelate dyes described in 10 above.

  12 11. An ink jet recording liquid comprising at least one metal chelate dye as described in 10 above.

  13. 13. An ink jet recording method, wherein the ink jet recording liquid according to 12 is sprayed on a recording medium for recording.

  14 11. A color toner comprising at least one metal chelate dye as described in 10 above.

  15. 11. A color filter comprising at least one metal chelate dye as described in 10 above.

  16. 11. An optical information recording medium comprising a recording layer containing at least one metal chelate dye described in 10 above.

  17. 17. An optical information recording method comprising recording information by irradiating the optical information recording medium according to 16 above with a laser beam selected from a range of 300 to 900 nm.

  According to the present invention, a novel metal-containing compound, a metal chelate dye and coloring composition from the metal-containing compound, an ink jet recording liquid containing the metal chelate dye, an ink jet recording method using the ink jet recording liquid, and the metal chelate It was possible to provide a color toner containing a dye, a color filter, an optical information recording medium, and an optical information recording method using the optical information recording medium.

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

  First, the compound represented by the general formula (1) according to the present invention will be described in detail.

In the general formula (1), R ₁ and R ₂ represent an alkyl group or a cycloalkyl group. Examples of the alkyl group represented by R ₁ and R ₂ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, and n-pentyl. Group, neopentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, An isohexadecyl group, n-octadecyl group, etc. can be mentioned. Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and the like.

The alkyl group or cycloalkyl group represented by R ₁ and R ₂ may have a substituent, and the substituent is not particularly limited. For example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group) Group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, trifluoromethyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), aryl group (eg 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 (eg vinyl Group, 2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group, cyclohexenyl group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom etc.), alkynyl group (eg, propargyl) Group), heterocyclic group (for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, etc.), arylsulfonyl group (for example, 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 A group (for example, an aminocarbonyl group, Tilaminocarbonyl group, dimethylaminocarbonyl group, butylaminocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl) Group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), sulfonamide group (for example, Methanesulfonamide group, benzenesulfonamide group, etc.), cyano group, alkoxy group (for example, methoxy group, ethoxy group, propoxy group, etc.) Aryloxy groups (eg, phenoxy group, naphthyloxy group, etc.), heterocyclic oxy groups, siloxy groups, acyloxy groups (eg, acetyloxy group, benzoyloxy group, etc.), sulfonic acid groups, sulfonic acid salts, aminocarbonyloxy Group, amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group), 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, dodecylureido group, Phenylureido Group, naphthylureido group, 2-pyridylaminoureido group, etc.), alkoxycarbonylamino group (eg, methoxycarbonylamino group, phenoxycarbonylamino group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl, etc.) ), Aryloxycarbonyl groups (for example, phenoxycarbonyl group, etc.), heterocyclic thio groups, thioureido groups, carboxyl groups, carboxylic acid salts, hydroxyl groups, mercapto groups, nitro groups, and the like. These substituents may be further substituted with the same substituent.

In the general formula (1), R ₁ 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-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, isotetradecyl group, n-hexadecyl group, isohexadecyl group, n-octadecyl group, iso Octadecyl group) is more preferable.

In general formula (1), R ₁ is most preferably a methyl group.

In the general formula (1), R ₂ is preferably an alkyl group, and an alkyl group having 11 to 18 carbon atoms (eg, n-undecyl group, n-dodecyl group, isotridecyl group, n-tetradecyl group, n-hexadecyl group, n -Octadecyl group, isotetradecyl group, isohexadecyl group, isooctadecyl group) are particularly preferred.

In the general formula (1), R ₃ represents a group represented by the general formula (2) or (3).

In the general formula (2), R ₄ represents a group represented by —CN or —LR ₁₀ . The group represented by —CN means a cyano group. L represents a divalent linking group containing at least one of an oxygen atom, a sulfur atom or a nitrogen atom. R ₁₀ represents a hydrogen atom or a substituent.

Oxygen atom represented by L, 2 divalent linking group containing at least one sulfur atom or nitrogen atom is not particularly limited, -O -, - S -, - CO -, - CO 2 -, - OCO -, - SO -, - SO 2 -, - CONR 11 --NR 12 CO -, - SO 2 NR 13 -, - NR 14 SO 2 -, - NR 15 CONR 16 -, - NR 17 CO 2 -, A divalent linking group selected from —OCONR ₁₈ —, —CONR ₁₉ SO ₂ —, and —SO ₂ NR ₂₀ CO— is preferable. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

The group represented by L is more preferably a divalent linking group selected from —CONR ₁₁ — and —NR ₁₂ CO—.

The substituent represented by R ₁₀ is not particularly limited, and examples thereof include the same groups as the substituents that the group represented by R ₁ and R ₂ in the general formula (1) may have. it can. These substituents may be further substituted with the same substituent. R ₁₀ is more preferably a hydrogen atom, an alkyl group or an aryl group.

In the general formula (2), R ₅ represents a substituent. The substituent represented by R ₅ is not particularly limited, and examples thereof include the same groups as the substituents that the group represented by R ₁ and R ₂ in the general formula (1) may have. Can do. These substituents may be further substituted with the same substituent.

In the general formula (2), m represents an integer of 0 to 4, and when m is 2 or more, the plurality of R ₅ may be the same or different.

In the general formula (3), R ₆ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. The group represented by R ₆ may have a substituent, and the substituent is not particularly limited. For example, the group represented by R ₁ and R ₂ in the general formula (1) has The same group as the substituent which may be mentioned can be mentioned. These substituents may be further substituted with the same substituent.

In general formula (3), R ₆ is preferably an aryl group.

  In the general formula (3), n represents an integer of 0 to 2, and n is preferably 2.

  Hereinafter, although the specific example of a compound represented by the said General formula (1) is shown, this invention is not limited by the following specific examples.

  Next, the metal-containing compound of the present invention will be described. The metal-containing compound of the present invention is represented by the following general formula (4) or (5) or a mixture of general formulas (4) and (5).

In the formula, M ²⁺ represents a divalent metal ion. R _1, R ₂ and R ₃ have the same meanings as R _1, R ₂ and R ₃ in formula (1). The metal ion represented by M ²⁺ is a divalent transition metal ion selected from the group VIII, Ib, IIb, IIIa, IVa, Va, VIa, and VIIa metal atoms. Specific examples include divalent metal ions of Ni, Cu, Co, Cr, Zn, Fe, Pd, and Pt, and more preferable examples include divalent metal ions of Ni, Cu, Co, and Zn. Ni divalent metal ions are preferred.

  The metal-containing compound of the present invention is obtained by reacting a divalent metal salt with the compound represented by the general formula (1). The method of synthesizing the metal-containing compound can be synthesized according to the method described in “Chelate Chemistry (5) Complex Chemistry Experimental Method (I) (Edited by Nanedo)” and the like. 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, Iron chloride (II), copper chloride (II), cobalt chloride, manganese chloride (II) are mentioned, preferably nickel chloride, nickel acetate, copper chloride, copper acetate, cobalt chloride, zinc chloride, zinc acetate, Most preferred is nickel acetate. The metal-containing compound of the present invention may have a neutral ligand depending on the central metal, and typical ligands include water, alcohols, and amines.

  Hereinafter, although the specific example of the metal containing compound obtained by making bivalent metal salt react with the compound represented by the said General formula (1) is shown, this invention is not limited by the following specific examples.

  Next, the chelatable dye will be described.

  The chelatable dye used in the present invention is not limited as long as it can chelate with a metal. Examples of such dyes include JP-A-61-227091, JP-A-63-145281, and JP-A-1 No. -63194, No. 3-114892, No. 4-89287, No. 4-158809, No. 4-164690, No. 4-241994, No. 4-34892, No. 5- No. 177958, No. 5-301470, No. 7-137455, No. 7-137467, No. 7-166084, No. 8-310135, No. 9-123620, No. 9-131973 No. 11-78258, JP-A 2000-255171, and 2002-234266. It is below.

  As described above, it is known that a metal chelate dye formed by 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, there is a merit in color reproduction such as an increase in molar extinction coefficient and a good color tone.

  As the yellow dye, the following general formula (6) is preferable.

In the formula, R ₂₁ and R ₂₂ represent a hydrogen atom or a substituent, R ₂₃ represents an alkyl group, and R ₂₄ represents a substituent. a represents an integer of 0 to 4, and when a is 2 or more, a plurality of R ₂₄ may be the same or different.

  As the magenta dye, the following general formula (7) is preferable.

In the formula, R ₃₁ and R ₃₂ represent a hydrogen atom or a substituent, and R ₃₃ represents an aryl group or an aromatic heterocyclic group which may have a substituent. X represents -CH = or -N =.

  Preferred examples of the cyan dye include the following general formula (8).

In the formula, R ₄₁ , R ₄₂ and R ₄₃ represent a hydrogen atom or a substituent, R ₄₄ and R ₄₅ represent an alkyl group, a cycloalkyl group or an aryl group, and R ₄₆ represents a substituent. b represents an integer of 0 to 4, and when b is 2 or more, the plurality of R ₄₆ may be the same or different.

  Hereinafter, although the specific example of the chelatable pigment | dye is shown, this invention is not limited by the following specific examples. These dyes can be synthesized according to the method described in the patent literature in which a dye capable of chelating with the metal is described.

  Next, a metal chelate dye obtained from at least one kind of dye chelatable with at least one kind of metal-containing compound obtained by reacting a divalent metal salt with the compound represented by the general formula (1), and the metal The coloring composition containing a chelate dye will be described.

  There is no limitation on the mixing ratio (molar ratio) of the metal-containing compound and the chelatable dye, and when dye: metal-containing compound = 1: X, X preferably represents 0.01 to 100, more preferably 0. 0.1 to 10, more preferably 0.3 to 1.

  The metal chelate dye is prepared by adding a metal-containing compound powder or a solution dissolved in an organic solvent to a solution obtained by dissolving or dispersing the dye in an organic solvent. 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.

  The metal chelate dye is preferably a structure represented by the following general formulas (9a) to (9i) or (10a) to (10c), but is not limited thereto.

Formula (9a) M ²⁺ AY ₂
Formula (9b) M ²⁺ AYZ
Formula (9c) M ²⁺ AZ ₂
Formula (9d) M ²⁺ A ₂ Y ₂
Formula (9e) M ²⁺ A ₂ YZ
Formula _{^{(9f) M 2+ A 2 Z}} 2
General formula (9 g) M ²⁺ A ₃ Y ₂
The general formula (9h) M ²⁺ A ₃ YZ
Formula _{^{(9i) M 2+ A 3 Z}} 2
Formula (10a) M ²⁺ BY
General formula (10b) M2 ⁺ BZ
Formula (10c) M ²⁺ B ₂

In the formula, A represents a chelatable dye, B represents a dye having a chelatable monovalent anion, and M ²⁺ represents a divalent metal ion. R _1, R ₂ and R ₃ have the same meaning as R _1, R ₂ and R ₃ in the general formula (1). These metal chelate dyes may have a neutral ligand depending on the central metal, and typical ligands include water, alcohols, and amines.

  Hereinafter, although the specific example of the metal chelate pigment | dye of the structure represented by general formula (9a)-(9i), (10a)-(10c) is shown, this invention is not limited by the following specific examples.

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

  The ink jet recording liquid containing at least one of the metal chelate dyes of the present invention may be one using only one kind of the metal chelate dye of the present invention or may be a combination of two or more metal chelate dyes. Moreover, it may be used in combination with a metal chelate dye outside the present invention.

  The ink jet recording liquid containing the metal chelate dye of the present invention can use various solvent systems such as an aqueous solvent, an oil-based solvent, and a solid (phase change) solvent. 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 as it is if the metal chelate dye of the present invention is soluble in the solvent system.

  On the other hand, when the metal chelate dye of the present invention is insoluble in the solvent system as it is, the metal chelate dye can be used in various dispersing machines (for example, ball mill, sand mill, attritor, roll mill, agitator mill, Henschel mixer, colloid mill, super Use a sonic homogenizer, pearl mill, jet mill, ang mill, etc.) or dissolve the metal chelate dye in a soluble organic solvent and then disperse it in the solvent system together with the polymer dispersant and surfactant. be able to. 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 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 a projected area of a transmission electron microscope (TEM) photograph (obtained for at least 100 particles or more) 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, it is preferable to dissolve the metal chelate dye in an organic solvent in which the metal chelate dye of the present invention is soluble and then disperse it in an aqueous solvent as a fine particle dispersion together with the oil-soluble 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 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, methylenemalonnitrile, 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. 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, malee 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 metal chelate dye 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, 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, tetrasenol, 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 (sucrose stearate, sucrose palmitate, saccharose behenate, saccharose laurate, saccharose melicate, 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 to 200 ° C, and more preferably 80 to 150 ° C.

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

  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.

  The ink jet recording liquid of the present invention in which the above-described water-based, oil-based, solid (phase change) solvent is used, or the metal chelate dye of the present invention is dissolved or dispersed, preferably has a viscosity during flight of 40 cps or less, and 30 cps or less. It is more preferable that

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

  The metal chelate dye 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 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 used, but can be preferably used as an ink jet recording liquid for an on-demand 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 metal chelate dye of the present invention. The content of the metal chelate dye of the present invention is preferably 2 to 30% by mass in the toner particles. In addition to the metal chelate dye of 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.

  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 a 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.

  In using the metal chelate dye of the present invention for color filters, when dispersing the metal chelate dye 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. In addition, conventionally known additives such as a dispersion aid, a smoothing agent, and an adhesive 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, 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 photosensitive coloring composition can be obtained by adding a photopolymerization initiator such as benzoin ether or benzophenone to the metal chelate dye of the present invention and the varnish, and then bricking it 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 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.

  Next, the optical information recording medium and the optical information recording method of the present invention will be described in detail.

  The metal chelate dye of the present invention used for the optical information recording medium of the present invention is a combination of two or more metal chelate dyes, even if only one type of the metal chelate dye of the present invention is used. Alternatively, it may be used in combination with a metal chelate dye outside the present invention. Further, the content of the metal chelate dye of the present invention in the recording layer is preferably 30 to 100% by mass, more preferably 60 to 100% by mass, and most preferably 90 to 100% by mass with respect to the dry mass of the entire recording layer. . Furthermore, in the recording layer of the present invention, a dye that can be used in a conventional optical information recording medium may be used in combination with the metal chelate dye in the present invention as long as the effect of the present invention is not affected.

  The optical information recording medium of the present invention includes various configurations. The optical information recording medium of the present invention has a configuration in which a recording layer, a light reflecting layer and a protective layer are arranged in this order on a disc-like substrate on which pregrooves having a constant track pitch are formed, or a light reflecting layer and a recording layer on the substrate. A structure having a layer and a protective layer in this order is preferable. In addition, two laminated bodies in which a recording layer and a light reflection layer are provided on a transparent disk-shaped substrate on which pregrooves having a constant track pitch are formed are bonded so that each recording layer is inside. The configuration is also preferable.

  The optical information recording medium of the present invention can use a substrate on which a pre-groove having a narrower track pitch is formed as compared with CD-R and DVD-R in order to achieve higher recording density. In the case of the optical information recording medium of the present invention, the track pitch is preferably in the range of 0.2 to 0.8 μm, more preferably in the range of 0.2 to 0.5 μm, particularly 0.2 to 0.5 μm. It is preferably in the range of 0.4 μm. The depth of the pregroove is preferably in the range of 0.01 to 0.18 μm, more preferably in the range of 0.01 to 0.15 μm, and particularly in the range of 0.02 to 0.15 μm. Is preferred. The width between adjacent pregrooves is preferably in the range of 0.05 to 0.4 μm, more preferably in the range of 0.08 to 0.3 μm, particularly in the range of 0.1 to 0.25 μm. Preferably there is.

  As an example of the optical information recording medium of the present invention, a manufacturing method having a recording layer, a light reflecting layer, and a protective layer in this order on a disc-like substrate will be described below.

  The substrate of the optical information recording medium of the present invention can be arbitrarily selected from various materials used as a substrate of a conventional optical information recording medium. Examples of substrate materials include acrylic resins such as glass, polycarbonate, and polymethyl methacrylate, vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers, epoxy resins, amorphous polyolefins, and polyesters. You may use them together. These materials can be used as a film or as a rigid substrate. Among the above materials, polycarbonate is preferable from the viewpoint of moisture resistance, dimensional stability, price, and the like.

  A subbing layer may be provided on the surface of the substrate on which the recording layer is provided for the purpose of improving flatness, improving adhesive force, and preventing alteration of the recording layer. Examples of the material for the undercoat layer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleic anhydride copolymer, polyvinyl alcohol, N-methylol acrylamide, styrene / vinyl toluene copolymer, chlorosulfone. Polymer materials such as chlorinated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate; and silane coupling And a surface modifier such as an agent. The undercoat layer is formed by dissolving or dispersing the above substances in an appropriate solvent to prepare a coating solution, and then applying this coating solution to the substrate surface by a coating method such as spin coating, dip coating, or extrusion coating. can do. The thickness of the undercoat layer is generally in the range of 0.005 to 20 μm, preferably in the range of 0.01 to 10 μm.

  The recording layer can be formed by a method such as vapor deposition, sputtering, CVD or solvent coating, and among these, solvent coating is preferred. In this case, the above-mentioned metal chelate dye, and optionally a quencher, a binder, etc. are dissolved in a solvent to prepare a coating solution, and then this coating solution is applied to the substrate surface to form a coating film and then dried. It can be carried out. Examples of the solvent of the coating solution include esters such as butyl acetate, ethyl lactate and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chloroform; dimethylformamide and the like Amides; Hydrocarbons such as methylcyclohexane; Ethers such as dibutyl ether, diethyl ether, tetrahydrofuran, dioxane; Alcohols such as ethanol, n-propanol, isopropanol, n-butanol, diacetone alcohol; 2,2,3,3-tetra Fluorinated solvents such as fluoropropanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, etc. And the like can be mentioned recall ethers. The above solvents can be used alone or in combination of two or more in consideration of the solubility of the metal chelate dye used. Various additives such as an antioxidant, a UV absorber, a plasticizer, and a lubricant may be further added to the coating solution depending on the purpose.

  In the case of using a binder, examples of the binder include natural organic polymer materials such as gelatin, cellulose derivatives, dextran, rosin and rubber; and hydrocarbon resins such as polyethylene, polypropylene, polystyrene and polyisobutylene, poly Vinyl resins such as vinyl chloride, polyvinylidene chloride, polyvinyl chloride / polyvinyl acetate copolymer, acrylic resins such as polymethyl acrylate and polymethyl methacrylate, polyvinyl alcohol, chlorinated polyethylene, epoxy resin, butyral resin, Examples include synthetic organic polymers such as rubber derivatives and initial condensates of thermosetting resins such as phenol / formaldehyde resins. When a binder is used in combination as a material for the recording layer, the amount of binder used is generally in the range of 0.01 to 50 times (mass ratio) with respect to the metal chelate dye, preferably 0.1 to 5 It is in the range of double amount (mass ratio). The concentration of the metal chelate dye in the coating solution thus prepared is generally in the range of 0.01 to 10% by mass, preferably in the range of 0.1 to 5% by mass.

  Examples of the coating method include a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, and a screen printing method. The recording layer may be a single layer or a multilayer. The thickness of the recording layer is generally in the range of 0.01 to 0.5 μm, preferably in the range of 0.015 to 0.3 μm, and more preferably in the range of 0.02 to 0.1 μm.

  The recording layer can contain various anti-fading agents in order to improve the light resistance of the recording layer. As the anti-fading agent, a singlet oxygen quencher is generally used. As the singlet oxygen quencher, those described in publications such as known patent specifications can be used. Specific examples thereof include JP-A Nos. 58-175893, 59-81194, 60-18387, 60-19586, 60-19586, 60-35054, 60-36190, 60-36191, 60-44554, 60-44555, 60-44389, 60-44390, 60-54892, 60-47069, 63-20995, JP 4-25492, JP-B-1-38680, and 6-26028, etc., German Patent No. 350,399, and Japanese Chemical Society Journal October 1992, page 1141, etc. Can be mentioned. As an example of a preferable singlet oxygen quencher, a compound represented by the following general formula (11) can be given.

However, R ₅₁ represents an alkyl group which may have a substituent, and Q ^- represents an anion. In the general formula (11), R ₅₁ is generally an optionally substituted alkyl group having 1 to 8 carbon atoms, and is preferably an unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of the substituent of the alkyl group include a halogen atom (eg, F, Cl), an alkoxy group (eg, methoxy, ethoxy), an alkylthio group (eg, methylthio, ethylthio), an acyl group (eg, acetyl, propionyl), an acyloxy group (Eg, acetoxy, propionyloxy), hydroxy group, alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), alkenyl group (eg, vinyl), and aryl group (eg, phenyl, naphthyl). Among these, a halogen atom, an alkoxy group, an alkylthio group, and an alkoxycarbonyl group are preferable. Preferred examples of the Q ⁻ anion include ClO ₄ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , and SbF ₆ ⁻ .

  Examples of compounds represented by the general formula (11) are shown in Table 1.

  The amount of the antifading agent such as the singlet oxygen quencher used is usually in the range of 0.1 to 50% by mass, preferably 0.5 to 45% by mass, based on the amount of the metal chelate dye of the present invention. More preferably, it is the range of 1-40 mass%, Most preferably, it is the range of 2-25 mass%.

  It is preferable to provide a light reflection layer adjacent to the recording layer for the purpose of improving reflectivity during information reproduction. The light-reflecting substance that is the material of the light-reflecting layer is a substance having a high reflectance with respect to laser light. Examples thereof include Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Si, Ge, Te, Pb, Po, Sn, Mention may be made of metals such as Bi and semi-metals or stainless steel. These substances may be used alone or in combination of two or more or as an alloy. Among these, Cr, Ni, Pt, Cu, Ag, Au, Al, and stainless steel are preferable. Particularly preferred are Au metal, Ag metal, Al metal or alloys thereof, and most preferred are Ag metal, Al metal or alloys thereof. The light reflecting layer can be formed on the substrate or the recording layer, for example, by vapor deposition, sputtering or ion plating of the light reflecting material. The thickness of the light reflecting layer is generally in the range of 0.01 to 0.3 μm, and preferably in the range of 0.05 to 0.2 μm.

A protective layer is preferably provided on the light reflecting layer or the recording layer for the purpose of physically and chemically protecting the recording layer and the like. In the case of adopting the same configuration as that for manufacturing a DVD-R type optical information recording medium, that is, a configuration in which two substrates are bonded with the recording layer inside, it is not always necessary to provide a protective layer. . Examples of materials used for the protective layer include inorganic substances such as Zn—SiO ₂ , ZnS, SiO, SiO ₂ , MgF ₂ , SnO ₂ , Si ₃ N ₄ , thermoplastic resins, thermosetting resins, and UV curable resins. Organic substances such as resins can be mentioned. The protective layer can be formed, for example, by laminating a film obtained by extrusion of plastic on the reflective layer via an adhesive. Or you may provide by methods, such as vacuum evaporation, sputtering, and application | coating. In the case of a thermoplastic resin or a thermosetting resin, it can also be formed by dissolving these in a suitable solvent to prepare a coating solution, and then applying and drying the coating solution. In the case of a UV curable resin, it can also be formed by preparing a coating solution as it is or by dissolving it in a suitable solvent, coating the coating solution, and curing it by irradiating with UV light. In these coating liquids, various additives such as an antistatic agent, an antioxidant, and a UV absorber may be added according to the purpose. The thickness of the protective layer is generally in the range of 0.1 μm to 1 mm. Through the above steps, it is possible to produce a laminate in which a recording layer, a light reflecting layer and a protective layer are provided on a substrate, or a light reflecting layer, a recording layer and a protective layer are provided on a substrate.

  The optical information recording method of the present invention is performed, for example, as follows using the optical information recording medium. First, recording light such as semiconductor laser light is irradiated from the substrate side or the protective layer side while rotating the optical information recording medium at a constant linear velocity (3.84 m / second in the case of DVD-R format) or a constant angular velocity. To do. By this light irradiation, the recording layer absorbs the light and the temperature rises locally, causing a physical or chemical change (for example, generation of pits) and changing its optical characteristics, thereby recording information. It is thought that it is done. In the present invention, semiconductor laser light having an oscillation wavelength in the range of 300 to 900 nm is used as recording light. As a preferable light source, a blue-violet semiconductor laser beam having an oscillation wavelength in the range of 400 to 410 nm, an infrared semiconductor laser beam having a central oscillation wavelength of 850 nm or 820 nm, and a central oscillation wavelength obtained by halving the wavelength using an optical waveguide element are each 425 nm. Alternatively, a 410 nm blue-violet SHG laser beam can be used. In particular, it is preferable to use blue-violet semiconductor laser light in terms of recording density. The information recorded as described above is reproduced by irradiating a semiconductor laser beam from the substrate side or the protective layer side while rotating the optical information recording medium at the same constant linear velocity as above and detecting the reflected light. Can be done by.

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

Example 1: Synthesis of exemplary metal-containing compound MS-2 Synthesis of exemplary compound 1-9

  To 80 ml of ethyl acetate, 5.0 g of anhydrous calcium chloride was added and cooled with water. To this, 8.1 g of compound AB was added, and 6.8 g of triethylamine was further added dropwise. After completion of the addition, the mixture was stirred at 45 to 50 ° C. for 1 hour. Then, after cooling with water, 9.4 g of compound AA was added dropwise, and the mixture was stirred for 1 hour after completion of the addition. After completion of the reaction, an aqueous hydrochloric acid solution was added to the reaction solution to dissolve the precipitated solid, followed by liquid separation, and the resulting organic layer was washed with water and concentrated under reduced pressure. The obtained residue was purified by column chromatography (developing solvent: ethyl acetate / n-hexane mixed solvent) to obtain 12.7 g of Exemplified Compound 1-9.

The results of ¹ H-NMR analysis of the resulting compound are as follows and confirmed to be Exemplified Compound 1-9.

¹ H-NMR (400 MHz, deuterated chloroform, δ (ppm)): 0.88 (t, 3H), 1.24 to 1.37 (m, 18H), 1.30 (s, 9H), 1 .68 (m, 2H), 2.12 (m, 2H), 2.33 (s, 3H), 2.89 (t, 2H), 3.98 (t, 2H), 4.19 (t, 2H), 6.82 (d, 2H), 7.40 (d, 2H).

  Synthesis of exemplary metal-containing compound MS-2

  At room temperature, 2.2 g of nickel (II) acetate tetrahydrate was dissolved in 27 ml of methanol, 9.5 g of Exemplified Compound 1-9 was added dropwise, and the mixture was stirred for 3 hours after completion of the dropwise addition. Thereafter, the mixture was ice-cooled, stirred for 1 hour under ice-cooling, and the precipitated solid was filtered. The obtained solid was recrystallized from 30 ml of methanol and 10 ml of acetonitrile mixed solvent to obtain 8.6 g of exemplary metal-containing compound MS-2. The melting point was 76-80 ° C.

  Similarly, the metal-containing compounds of the present invention described in Table 2 below were synthesized. The melting point is also shown.

Example 2
Below, the preparation method of the metal chelate pigment | dye obtained from the pigment | dye which can be chelated with the metal containing compound obtained by making bivalent metal salt react with the compound represented by the said General formula (1) is shown.

(Method for producing metal chelate dye (metal chelate dye 1) of metal-containing compound MS-2 and dye Y-1)
1 g of dye Y-1 was dissolved in 50 ml of acetone, 1.8 g of a metal-containing compound MS-2 was added thereto, and reacted for 1 hour under heating and reflux. After completion of the reaction, the target metal chelate dye 1 was synthesized by distilling off the solvent. When the spectral absorption spectrum of the obtained metal chelate dye 1 in acetone was measured, the maximum absorption wavelength was 455 nm.

  Similarly, metal chelate dyes obtained from dyes capable of chelating with metal-containing compounds described in Table 3 below were prepared. The maximum absorption wavelength of the obtained metal chelate dye is also shown.

Example 3
(Preparation of fine particle dispersion)
5 g of a colored composition containing a metal chelate dye (molar ratio; dye: metal-containing compound = 1: 0.5) obtained from the dye and the metal-containing compound shown in Table 4 (BL- manufactured by Sekisui Chemical Co., Ltd.) S, average polymerization degree 350) and 50 g of ethyl acetate were put into a separable flask, and the inside of the flask was substituted with N _2, followed by stirring to completely dissolve the polymer and the colored composition. 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 colored composition of the present invention. 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 colored fine particle dispersion in which the content of the coloring composition 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, Prepare and mix Surfynol 465 to 0.3% by mass and the remaining pure water, and filter through a 2 μm membrane filter to remove dust and coarse particles. As shown in Table 4, inkjet ink 1 ~ 21 was obtained.

(Sample preparation and evaluation)
Furthermore, each ink was printed on Konica photo jet paper Photolique QP glossy paper (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 4.

(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).

  << Structures of dyes and comparative metal-containing compounds used >>

  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 weight of a polyester resin, a coloring composition containing a metal chelate dye (molar ratio; dye: metal-containing compound = 1: 0.5) obtained from a dye and a metal-containing compound described in Table 5 or a simple dye (colorant) 8 parts by mass 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 12 by a pulverization method.

<Manufacture of color toner: polymerization method>
A metal chelate dye (molar ratio; dye: metal-containing compound = 1: 0.5) obtained from the dyes and metal-containing compounds listed in Table 5 is contained in an aqueous solution in which 5 g of sodium dodecyl sulfate is dissolved in 200 ml of pure water. An aqueous dispersion of a colorant is prepared by adding 20 g of a coloring composition or a simple pigment (colorant), stirring and applying ultrasonic waves, and the aqueous dispersion of this colorant and a low molecular weight polypropylene (number average molecular weight = 3200) was heated in advance, and an emulsified dispersion emulsified in water so as to have a solid concentration of 30% by mass with a surfactant 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 toner 13 was obtained by polymerization.

  Further, color toner 14 to color toner 24 were obtained in the same manner as color toner 13 except that the color composition and colorant described in Table 5 were used instead of the color composition of the present invention.

<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, hue, light fastness, and transparency of an OHP image were evaluated.

《Hue》
The hue was evaluated visually.

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

《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.) with reference to an OHP sheet on which no color toner is carried, yellow 570 nm, Spectral transmittances at magenta 650 nm and cyan 500 nm were obtained.

○: 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 5 shows the evaluation results of hue, light fastness, and transparency of the OHP image.

  As is apparent from Table 5, an image produced using the color toner of the present invention exhibits faithful color reproduction and high OHP quality, and the color toner of the present invention is suitable for use as a full color 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>
Mole ratio: Y-1: MS-2 = 1: 0.5 metal chelate dye 10 parts Photosensitive polyimide resin varnish 50 parts N-methyl-2-pyrrolidone 40 parts A glass plate treated with a silane coupling agent It was set on a spin coater, and the above-mentioned photosensitive coating agent for CF-1 color filter 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.

  Similarly, using a metal chelate dye having a molar ratio of M-1: MS-2 = 1: 0.5, a magenta mosaic pattern is also obtained, and a molar ratio; C-1: MS-2 = 1: A cyan mosaic pattern was formed using a metal chelate dye consisting of 0.5.

  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.

Example 6
A colored composition containing a metal chelate dye (molar ratio; dye: metal-containing compound = 1: 0.5) obtained from the dye and the metal-containing compound shown in Table 6 to 2,2,3,3-tetrafluoropropanol This was dissolved to obtain a recording layer forming coating solution (concentration: 1 mass%). A polycarbonate substrate (diameter: 120 mm, thickness) on which a spiral pre-groove (track pitch: 0.4 μm, groove width: 0.2 μm, groove depth: 0.05 μm) is formed by injection molding on the surface of this coating solution. The recording layer (thickness (inside the pregroove): about 80 nm) was formed on the surface of the pregroove side having a thickness of 0.6 mm by spin coating.

  Next, silver was sputtered on the recording layer to form a light reflecting layer having a thickness of about 100 nm. Further, a UV curable resin (SD318, manufactured by Dainippon Ink & Chemicals, Inc.) was applied on the light reflecting layer and cured by irradiating with ultraviolet rays to form a protective layer having a layer thickness of 7 μm.

  Optical discs (optical information recording media) 1 to 3 of the present invention were obtained by the above steps (the amount of the colored composition used was the same).

(Method for producing metal chelate dye of dye DD and metal-containing compound MS-2)
1 g of the dye D-D was dissolved in 50 ml of acetone, 1.5 g of the metal-containing compound MS-2 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 to synthesize the target metal chelate dye.

[Evaluation as optical information recording medium (optical disc)]
A 14T-EFM signal was recorded on the optical disk produced above at a linear velocity of 3.5 m / sec using a blue-violet semiconductor laser beam having an oscillation wavelength of 405 nm, and the recorded signal was reproduced. The degree of modulation at optimum power (larger value is better), groove reflectance (larger value is better), and sensitivity (smaller value is better) were measured. Recording and recording characteristic evaluation were performed using DDU1000 manufactured by Pulstec Industrial Co., Ltd. The evaluation results are shown in Table 6.

  << Structure of dye used >>

  From the results shown in Table 6, the optical disk having the recording layer containing the coloring composition of the present invention exhibits a higher reflectivity with respect to the blue-violet semiconductor laser light than the comparison, and gives a high degree of modulation. It turns out that it is sensitivity.

Claims (17)

A metal-containing compound obtained by reacting a divalent metal salt with a compound represented by the following general formula (1).

(In the formula, R ₁ and R ₂ represent an alkyl group or a cycloalkyl group, and R ₃ represents a group represented by the following general formula (2) or (3)).

(In the formula, R ₄ represents a group represented by —CN or —LR ₁₀ , L represents a divalent linking group containing at least one of an oxygen atom, a sulfur atom or a nitrogen atom, and R ₁₀ represents R ₅ represents a substituent, m represents an integer of 0 to 4, and when m is 2 or more, a plurality of R ₅ may be the same or different. )

(In the formula, R ₆ represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and n represents an integer of 0 to 2.) In the general formula (1), the group represented by R ₃ represents the general formula (2), and the group represented by R ₄ in the general formula (2) is a group represented by —CN. The metal-containing compound according to claim 1, wherein In the general formula (1), the group represented by R ₃ represents the general formula (2), and the group represented by R ₄ in the general formula (2) is represented by -LR _10. The metal-containing compound according to claim 1, wherein In the general formula (1), the group represented by R ₃ represents the general formula (2), and the divalent linking group represented by L in the general formula (2) is —O— or —S—. , —CO—, —CO ₂ —, —OCO—, —SO—, —SO ₂ —, —CONR ₁₁ ——NR ₁₂ CO—, —SO ₂ NR ₁₃ —, —NR ₁₄ SO ₂ —, —NR ₁₅ CONR ₁₆ −, —NR ₁₇ CO ₂ —, —OCONR ₁₈ —, —CONR ₁₉ SO ₂ —, —SO ₂ NR ₂₀ CO— (R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , and R ₂₀ each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. Compound. In Formula (1), based on said general formula represented by R ₃ represents a (3), and metal-containing according to claim 1, characterized in that n in the general formula (3) is 2 Compound. In the general formula (1), the group represented by R ₃ represents the general formula (3), and the group represented by R ₆ in the general formula (3) is an aryl group. Item 6. The metal-containing compound according to Item 1 or 5. In the said General formula (1), group represented by R < ₁ > is a linear alkyl group, The metal containing compound of any one of Claims 1-6 characterized by the above-mentioned. The metal-containing compound according to claim 7, wherein the linear alkyl group represented by R ₁ is a methyl group. In Formula (1), a metal-containing compound according to any one of claims 1 to 8, the groups represented by R ₂ is equal to or an alkyl group having 11 to 18 carbon atoms. The metal chelate pigment | dye obtained from at least 1 type of the chelate which can chelate with at least 1 type of the metal containing compound of any one of Claims 1-9. A coloring composition comprising at least one metal chelate dye according to claim 10. An ink jet recording liquid comprising at least one metal chelate dye according to claim 10. An ink jet recording method comprising: spraying the ink jet recording liquid according to claim 12 on a recording medium for recording. A color toner comprising at least one metal chelate dye according to claim 10. A color filter comprising at least one metal chelate dye according to claim 10. An optical information recording medium comprising a recording layer containing at least one of the metal chelate dyes according to claim 10. 17. An optical information recording method comprising: recording information by irradiating the optical information recording medium according to claim 16 with a laser beam selected from a range of 300 to 900 nm.