JP2010096819A - Toner for electrophotograph and metal-containing compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner for electrophotograph which has good hue, high light fastness and stable charging characteristics without causing voids in an image. <P>SOLUTION: The toner contains one kind of compound expressed by general formula (1). In the formula: M represents a divalent metal ion; R<SB>1</SB>and R<SB>2</SB>represent an aryl group, an alkenyl group, etc.; R<SB>3</SB>represents an alkyl group of a branch, etc. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an electrophotographic toner and a metal-containing compound, and more particularly to an electrophotographic toner using a metal ion supply compound.

  Color copier (registered trademark) using electrophotography and electrophotographic toners used in color printers include color reproducibility, image transparency, and light resistance. The electrophotographic toner in which the pigment used is dispersed in the particles as a colorant is excellent in light resistance because of the use of the pigment. However, since the colorant is insoluble, it easily aggregates, and the transparency decreases. The hue change of the transmitted color is a problem. Thus, toners in which the colorant is changed from a pigment to a dye have been disclosed (for example, see Patent Document 1). However, these toners have a problem in light resistance, although they are excellent in transparency and hue change. Since a very general dye has a relatively low molecular weight, it sublimates during heat fixing, and has the disadvantage of causing contamination on the surface of the fixing roller and the printer, reduction in image density, blurring, and the like. In order to solve these drawbacks, in recent years, a toner using a metal complex dye as a colorant has been disclosed (for example, see Patent Document 2). However, a toner containing the metal complex dye described above is light resistant. However, further improvement has been desired such as low reflection and different reflection spectra after printing due to aggregation and the like.

  These problems were greatly improved by an electrophotographic toner using a metal-containing compound (see, for example, Patent Document 3), and an image obtained from this toner was excellent in color reproducibility and light resistance.

  In addition, the toner for electrophotography is usually produced by a kneading and pulverizing method in which a binder resin is melt-kneaded together with a pigment and, if necessary, a release agent such as wax or a charge control agent, and then finely pulverized and further classified. Yes.

  The toner obtained by the usual kneading and pulverization method is generally indefinite, its particle size distribution is broad, low fluidity, low transferability, high fixing energy, and non-uniform charge amount among toner particles However, there is a problem that charging stability is low. Furthermore, the image obtained from such toner is still unsatisfactory in image quality.

  On the other hand, in order to overcome the problems of the toner by the kneading and pulverizing method, a method for producing the toner by the polymerization method has been proposed. Since this method does not include a pulverization step, the toner does not require a kneading step and a pulverization step, which contributes to cost savings such as energy saving, production time reduction, and product yield improvement. large. In addition, the particle size distribution of the polymerized toner particles obtained by such a polymerization method is easy to form a sharp distribution as compared with the particle size distribution of the toner by the pulverization method, and it is easy to encapsulate the wax, and the fluidity of the toner Can be greatly improved. It is also easy to obtain a spherical toner.

  However, there are many problems that have not yet been solved in the toner produced by the polymerization method. For example, even if the toner obtained by the above method is washed at the time of manufacture, the surfactant remains in the toner particles. Therefore, when the toner is used or stored under high temperature and high humidity, the toner particles absorb moisture and charge rising As a result, the image quality and the charging stability deteriorated, so that voids and fogging occurred on the image, dot reproducibility and fine line reproducibility decreased, and image quality deteriorated. In particular, when forming a full-color image in which a plurality of toner images are overlaid, the occurrence of voids and fogging was noticeable on the image. (For example, refer to Patent Document 4).

From such a background, there has been a demand for a toner that sufficiently satisfies color reproducibility and light resistance, has good water resistance and charging stability, and has no image void.
JP-A-3-276161 Japanese Patent Laid-Open No. 10-20559 JP 2007-34264 A JP 2004-302066 A

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a good electrophotographic toner which has a good hue and light resistance and is free from chargeability and image dropout.

  As a result of intensive studies to solve the above problems, the present inventor has a specific metal-containing compound in a stable dispersion state in an electrophotographic toner, thereby having a good hue, light resistance, It was confirmed that an electrophotographic toner having good water resistance and charging stability and having no image void when an image was formed was obtained, and the present invention was completed. That is, the above object of the present invention can be achieved by the following configuration.

  1. An electrophotographic toner comprising at least one metal-containing compound represented by the following general formula (1):

[Wherein, M represents a divalent metal ion, R ₁ represents an aryl group, an alkenyl group, an alkynyl group or a 6-membered aromatic heterocyclic group, and R ₂ represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. Group, aryl group, heterocyclic group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, halogen atom or cyano group, R ₃ represents a branched alkyl group , An alkenyl group, an alkynyl group, or a group containing a ring structure. ]
2. 2. The electrophotographic toner according to 1 above, wherein the group represented by R ₁ in the general formula (1) is substituted with at least one electron-withdrawing group.

3. 3. The electrophotographic toner according to 1 or 2, wherein M in the general formula (1) is Cu ²⁺ .

4). 4. The electrophotographic toner according to any one of 1 to 3, wherein R ₃ in the general formula (1) is a group containing a ring structure.

  5. 5. A metal-containing compound, wherein the metal compound that can be used in the electrophotographic toner described in any one of 1 to 4 is represented by the following general formula (2).

[Wherein, R _a1 represents an aryl group, an alkenyl group, an alkynyl group, or a 6-membered aromatic heterocyclic group, and R _a2 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, or an alkoxy group. A carbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a halogen atom or a cyano group is represented, and R _a3 represents a group containing a ring structure. ]

  According to the present invention, it is possible to provide an electrophotographic toner having a good hue, excellent light resistance, water resistance, and charging stability, and having no image omission when an image is formed.

  The present invention will be described in more detail. The structure represented by the general formula (1) will be described.

<< Compound Represented by Formula (1) >>
The general formula (1) of the present invention can also be expressed using the following limit structural formulas of the following general formula (1a) and general formula (1b). In the present invention, the general formula (1), the general formula (1a) and the general formula (1b) are essentially the same and are not distinguished. The distinction between a covalent bond (indicated by −) and a coordination bond (indicated by...) Is also formal, and does not represent an absolute distinction.

The metal-containing compound in the present invention is preferably obtained by synthesizing a compound of the following general formula (1-2) and then reacting with a divalent metal compound. The method for synthesizing these metal-containing compounds can be synthesized in accordance with the method described in “Chelate Chemistry (5) Complex Chemistry Experimental Method [I] (Edited by Nanedo)”. Divalent metal compounds used include nickel chloride, nickel acetate, magnesium chloride, calcium chloride, barium chloride, zinc chloride, zinc acetate, titanium chloride (II), iron chloride (II), copper chloride (II), Examples include cobalt chloride, manganese (II) chloride, lead chloride, lead acetate, mercury chloride, mercury acetate, copper perchlorate, etc. As mentioned above, the color of the metal-containing compound itself and the color tone of the chelated dye To zinc chloride, zinc acetate, nickel chloride, nickel acetate, copper chloride, copper acetate, copper perchlorate, and most preferably copper acetate. The metal-containing compound used in the present invention may have a neutral ligand depending on the central metal, and typical ligands include H ₂ O or NH ₃ .

  In the general formulas (1), (1a), and (1b), M represents a divalent metal ion, preferably a divalent transition metal ion. Among divalent transition metal ions, nickel, copper, and zinc are preferable, and copper is most preferable from the color of the metal-containing compound itself and the color tone of the pigment that interacts with the general formula (1).

In general formula (1), general formula (1a), general formula (1b), and general formula (1-2), R ₁ is an aryl group (for example, phenyl group, naphthyl group, etc.), an alkenyl group (for example, vinyl group). , An allyl group, etc.), an alkynyl group (eg, ethynyl group, propargyl group, etc.), or a 6-membered aromatic heterocyclic group (eg, pyridyl group, pyranyl group, etc.), which further has a substituent. Also good.

Examples of the substituent that can be substituted for R ₁ include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, Tetradecyl group, pentadecyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), aryl group (eg, phenyl group, naphthyl group) Etc.), heteroaryl group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group , Phthalazyl group, etc.), heterocyclic group (for example, pyro Lysyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, cyclopentyloxy group, cyclohexyl) Oxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), alkylthio group (eg methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, cyclopentylthio group, Cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, Tiloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, Butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group) Ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, Decylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy) Group), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group) , Dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methyla Minocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido Group), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethyl) Hexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl) Group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino) Group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), cyano group, nitro group, halogen atom (for example, chlorine atom, bromine atom) Fluorine atom, can be mentioned an iodine atom, etc.), these groups may be further substituted by a similar group.

R ₁ is preferably an aryl group and a 6-membered aromatic heterocyclic group. Of the substituents substituted for R ₁ , at least one is preferably an electron-withdrawing group, and a preferred electron-withdrawing group has a Hammett's substituent constant (σp value) of 0.1 or more and 0.9 or less. An electron withdrawing group is mentioned.

  A substituent having a σp value of 0.1 or more and 0.9 or less will be described. As the value of Hammett's substituent constant σp here, Hansch, C .; It is preferable to use the values described in the report of Leo et al. (For example, J. Med. Chem. 16, 1207 (1973); ibid. 20, 304 (1977)).

  For example, as a substituent or atom having a value of σp of 0.10 or more, a chlorine atom, a bromine atom, an iodine atom, a carboxyl group, a cyano group, a nitro group, a halogen-substituted alkyl group (for example, trichloromethyl, trifluoromethyl, Chloromethyl, trifluoromethylthiomethyl, trifluoromethanesulfonylmethyl, perfluorobutyl), aliphatic / aromatic or heterocyclic acyl groups (eg, formyl, acetyl, benzoyl), aliphatic / aromatic or heterocyclic sulfonyl groups (eg, , Trifluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl), a carbamoyl group (eg, carbamoyl, methylcarbamoyl, phenylcarbamoyl, 2-chlorophenylcarbamoyl), an alkoxycarbonyl group (eg, methoxycarbonyl, Xyloxycarbonyl, diphenylmethylcarbonyl), substituted aromatic groups (eg, pentachlorophenyl, pentafluorophenyl, 2,4-dimethanesulfonylphenyl, 2-trifluoromethylphenyl), heterocyclic residues (eg, 2-benzooxa Zolyl, 2-benzthiazolyl, 1-phenyl-2-benzimidazolyl, 1-tetrazolyl), azo group (eg, phenylazo), ditrifluoromethylamino group, trifluoromethoxy group, alkylsulfonyloxy group (eg, methanesulfonyloxy) ), Acyloxy groups (eg acetyloxy, benzoyloxy), arylsulfonyloxy groups (eg benzenesulfonyloxy), phosphoryl groups (eg dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl groups (eg For example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl) Is mentioned.

  Examples of the substituent having a σp value of 0.35 or more include a cyano group, a nitro group, a carboxyl group, a fluorine-substituted alkyl group (for example, trifluoromethyl, perfluorobutyl), an aliphatic / aromatic or heterocyclic acyl group. (Eg, acetyl, benzoyl, formyl), aliphatic / aromatic or heterocyclic sulfonyl groups (eg, trifluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl), alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, diphenylmethylcarbonyl) , Fluorine or sulfonyl group-substituted aromatic group (eg, pentafluorophenyl, 2,4-dimethanesulfonylphenyl), heterocyclic residue (eg, 1-tetrazolyl), azo group (eg, phenylazo), alkylsulfonyloxy group (example , Methanesulfonyloxy), a phosphoryl group (e.g., dimethoxyphosphoryl, diphenylphosphoryl), a sulfamoyl group.

  Examples of the substituent having a value of σp of 0.60 or more include a cyano group, a nitro group, an aliphatic / aromatic or heterocyclic sulfonyl group (for example, trifluoromethanesulfonyl, difluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl) and the like. It is done.

The electron-withdrawing group substituted for R ₁ is preferably a halogen atom, a halogenated alkyl group (particularly a fluorine-substituted alkyl group), an acyl group, a cyano group, a nitro group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfonyl group. It is an oxy group.

R ₂ is a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, halogen atom Or a cyano group, and examples of each include the same synonymous groups in the examples of the substituent that can be substituted with R ₁ described above.

R ₂ is preferably a heterocyclic group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group or a cyano group, more preferably an alkoxycarbonyl group, an acyl group or a cyano group.

R ₃ represents a branched alkyl group (eg, isopropyl group, tert-butyl group, 2-ethylhexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), Or represents a group containing a ring structure.

The group containing a ring structure in the present invention only needs to contain a ring structure at an arbitrary position in R ₃ , and examples of the ring structure include an aryl group (for example, a phenyl group, a naphthyl group, etc.). , A cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), a heteroaryl group (eg, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group) Benzoimidazolyl group, benzooxazolyl group, quinazolyl group, phthalazyl group, etc.), heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), and R ₃ is preferably
General formula (3) * -LR ₄
It is group represented by these.

In the general formula (3), L is an alkylene group having 1 to 15 carbon atoms, —SO ₂ O—, —OSO ₂ —, —SO ₂ —, —CO—, —O—, —S—, —SO _2. This represents a group formed by combining a divalent linking group selected from NH-, -NHSO _2- , -CONH-, -NHCO-, -COO-, and -OOC- alone, or a combination thereof. Bonded to the oxygen atom adjacent to R ₃ in 1).

L may have a substituent, and examples of the substituent include a group having the same meaning as the substituent that can be substituted with R ₁ in the general formula (1).

The divalent linking group represented by L is preferably an alkylene group or a group containing an alkylene group. The group containing an alkylene group only needs to contain an alkylene group at an arbitrary position in the divalent linking group represented by L. Specifically, the alkylene group, —SO ₂ O—, —OSO _{2 -, - SO 2 -, -} CO -, - O -, - S -, - SO 2 NH -, - NHSO 2 -, - CONH -, - NHCO -, - COO -, - OOC- 2 divalent selected from Is a group containing an alkylene group in the structure of a group formed by combining one or more linking groups.

Specific examples of the divalent linking group represented by L are shown below, but the present invention is not limited thereto. L is * and is bonded to an oxygen atom adjacent to R ₃ in the general formula (1) or R ₄ .

R ₄ represents an aryl group (for example, phenyl group, naphthyl group, etc.), a cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), a heteroaryl group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group). , Pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, etc.), heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group) Etc.).

R ₃ and R ₄ may have a substituent, and examples of the substituent include a group having the same meaning as the substituent that can be substituted for R ₁ in the general formula (1).

Preferable substituents for substituting L, R ₃ and R ₄ include alkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, acyl group, acyloxy group, Amido group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, amino group, cyano group, nitro group, halogen atom, more preferably alkyl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group , Sulfamoyl group, acyl group, acyloxy group, amide group and carbamoyl group, and particularly preferred groups are alkyl group, alkoxy group, aryloxy group, alkoxycarbonyl group, acyloxy group and amide group.

R ₃ is preferably a branched alkyl group or a group containing a ring structure, and more preferably a group containing a ring structure.

R ₄ is preferably a phenyl group, a cycloalkyl group, or a heteroaryl group, more preferably a phenyl group or a cycloalkyl group, and particularly preferably a phenyl group.

R _a1 and R _a2 in the general formula (2) each represent the same group as R ₁ and R _{2 in} the general formula (1), and preferred groups are also the same groups.

R _a3 in the general formula (2) is the same group as the group containing the ring structure of R ₃ in the general formula (1), and preferred substituents are also the same group.

  Specific examples of the metal-containing compound represented by the general formula (1) are shown below, but the present invention is not limited thereto. * In the table indicates the bonding position of each group.

<< Method for Synthesizing Compound Represented by Formula (1) >>
Synthesis example 1
<Synthesis of Exemplified Compound 5>

Synthesis of Compound B In a 500 ml three-necked flask, 90 g of Compound A, 21.5 g of cyanoacetic acid, 1.31 g of p-toluenesulfonic acid monohydrate and 300 ml of toluene were added and dehydrated using an ester tube. The mixture was heated and refluxed for 2 hours, the solvent was distilled off under reduced pressure, 500 ml of acetone was added and recrystallized to obtain 94.4 g of Compound B.

Synthesis of Compound C 5 g of Compound B, 25 ml of toluene, 3.3 g of triethylamine and 2.42 g of calcium chloride were added to a 100 ml three-necked flask and heated to 80 ° C. and stirred. After the internal temperature reached 80 ° C., 2.74 g of 3,4-dichlorobenzoyl chloride was added dropwise over 1 h. After completion of the dropwise addition, the mixture was cooled, separated with hydrochloric acid, neutralized with pure water, and the solvent was distilled off. The compound C was obtained by recrystallization by adding 50 ml of toluene and 50 ml of ethyl acetate ( ¹ H-NMR, CDCl ₃ δ = 0.88 (t, 3H), δ = 1.20-1.28). (M, 28H), δ = 1.42 (m, 2H), δ = 1.76 (m, 2H), δ = 3.01 (t, 2H), δ = 3.93 (t, 2H), δ = 4.48 (t, 2H), δ = 6.87 (d, 2H), δ = 7.19 (d, 2H), δ = 7.60 (d, 1H), δ = 7.91 ( dd, 2H), δ = 8.07 (d, 2H), δ = 14.17 (s, 1H)).

Synthesis of Exemplified Compound 5 2 g of Compound C and 80 ml of acetone were added to a 200 ml three-necked flask and heated and stirred until the internal temperature reached 55 ° C. Thereafter, 0.38 g of copper acetate monohydrate was dissolved in 5 ml of a solvent of MeOH / water = 5/1 and added dropwise over 30 minutes. After completion of the dropwise addition, 2.0 g of Exemplified Compound 5 was obtained by filtering the precipitated solid (melting point: 186 ° C.).

Synthesis example 2
<Synthesis of Exemplified Compound 31>

Synthesis of Compound E 36.11 g of Compound D, 7.8 g of cyanoacetic acid, 1.6 g of p-toluenesulfonic acid monohydrate and 180 ml of toluene were added to a 300 ml three-necked flask and dehydrated using an ester tube. Then, the mixture was heated and refluxed for 2 hours, separated with pure water to neutralize the pH, and then the solvent was distilled off under reduced pressure to obtain 41.18 g of Compound E.

Synthesis of Compound F 20 g of Compound E, 200 ml of toluene, 11.1 g of triethylamine, and 8.2 g of calcium chloride were added to a 500 ml three-necked flask, and the mixture was cooled to 8 ° C. and stirred. After the internal temperature reached 8 ° C., 2.20 g of 4-methoxycarbonylbenzoyl chloride was added dropwise over 30 minutes. After completion of dropping, the solution was separated three times with 100 ml of pure water, and the solvent was distilled off under reduced pressure. Purification by column chromatography using toluene / ethyl acetate as a developing solvent gave 20.15 g of Compound F. ( ¹ H-NMR, CDCl ₃ δ = 0.88 (t, 3H), δ = 1.20-1.28 (m, 28H), δ = 1.44 (m, 2H), δ = 1.57 (S, 9H), δ = 1.81 (m, 2H), δ = 2.10 (m, 2H), δ = 2.28 (s, 3H), δ = 2.67 (m, 2H), δ = 3.79 (m, 2H), δ = 3.96 (s, 3H), δ = 4.37 (m, 2H), δ = 8.07 (d, 2H), δ = 6.96 ( d, 2H), δ = 8.05-8.18 (dd, 4H), δ = 14.23 (s, 1H)).

Synthesis of Exemplary Compound 31 2 g of Compound F and 20 ml of acetone were added to a 50 ml three-necked flask, and the internal temperature was heated to 55 ° C. and stirred. 0.34 g of copper acetate monohydrate was dissolved in 5 ml of a solvent of MeOH / water = 1/1 and added dropwise to the reaction solution. After completion of dropping, the mixture was cooled with ice water, and the precipitated solid was filtered to obtain 1.8 g of Exemplified Compound 31. (Melting point: 62 ° C)
Other compounds can be synthesized in the same manner.

  <Synthesis of Comparative Compounds 1 and 2>

  Comparative compounds 1 and 2 were synthesized in the same manner as in Synthesis Example 1.

  When the metal-containing compound of the present invention is used by adding it to an electrophotographic toner, at least one chelateable dye is used for image formation. The chelatable dye only needs to be capable of chelating with the metal-containing compound of the present invention. Examples of such a dye include JP-A-3-114892, JP-A-4-62092, JP-A-4-62094, Examples thereof include the dyes described in JP-A-4-82896, JP-A-5-16545, JP-A-5-177958, and JP-A-5-301470.

  The yellow dye is preferably a dye represented by the following general formula (4).

In the formula, each of R ₁₁ and R ₁₂ represents a hydrogen atom or a substituent, R ₁₃ represents an alkyl group or an aryl group which may have a substituent, and Z is a 5- to 6-membered member together with 2 carbon atoms. Represents an atomic group necessary for constituting the aromatic ring.

  For the dye represented by the general formula (4), for example, a compound represented by the following general formula (A) can be obtained from Chemical Reviews, Vol. 75,241 (1975) and can be produced according to a known coupling reaction with a compound represented by the following general formula (B).

_Wherein, R _11, R _{12, R 13} and Z have the same meanings as _{R 11,} R _{12, R 13} and Z of the general formula (4).

  Although the typical example of the yellow pigment | dye represented by General formula (4) below is shown, this invention is not limited to these.

  Preferably, the magenta dye includes a dye represented by the following general formula (5).

In the formula, R ₂₁ represents a hydrogen atom, a halogen atom or a substituent, and R ₂₂ represents an optionally substituted aromatic carbocyclic group or aromatic heterocyclic group. X represents a methine group or a nitrogen atom. R ₂₃ represents the following general formula (6) or (7), X ′ represents a carbon atom or a nitrogen atom, and Y represents an atomic group forming a nitrogen-containing aromatic heterocycle. W represents an atomic group forming an aromatic carbocycle or an aromatic heterocycle, and R ₂₄ represents an alkyl group.

  The dye represented by the general formula (5) can be synthesized according to a conventionally known method. For example, the azomethine dye in the general formula (5) can be synthesized according to the oxidative coupling method described in JP-A-63-113077, JP-A-3-275767, and 4-89287.

  Specific examples of the magenta dye represented by the general formula (5) are shown below, but the present invention is not limited thereto.

  The cyan dye is preferably a dye of the following general formula (8).

In the formula, R ₃₁ and R ₃₂ each represent a substituted or unsubstituted aliphatic group, and R ₃₃ represents a substituent. n represents an integer of 0 to 4, and when n is 2 or more, the plurality of R ₃₃ may be the same or different. R ₃₄ , R ₃₅ and R ₃₆ all represent an alkyl group, but R ₃₄ , R ₃₅ and R ₃₆ may be the same or different. _{However, R 35} and _{R 36} is an alkyl group having 3 to 8 carbon atoms.

  The dye represented by the general formula (8) can be synthesized according to a conventionally known method. For example, it can be synthesized according to the oxidative coupling method described in JP-A Nos. 2000-2255171, 2001-334755, 2002-234266 and the like.

  Specific examples of the cyan dye represented by the general formula (8) are shown below, but the present invention is not limited thereto.

  The metal chelate dye comprising the metal-containing compound represented by the general formula (1) and the dye represented by the general formula (4), (5) or (8) is represented by the following general formula (9), (10 ) Or (11).

In the general formulas (9) to (11), R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ and R ₃₅ are each represented by the above general formula. It is synonymous with the substituent as described in (4), (5) and (8). R ₁ , R ₂ and R ₃ are each synonymous with the substituent described in the general formula (1), and M ²⁺ represents a divalent metal ion.

  The chelate dye used in the present invention can be used for various purposes other than the toner for electrophotography. For toner, it can be used according to the methods described in JP-A-10-265690, JP-A-2000-345059, etc., but the usage and usage of the dye of the present invention are limited to these. It is not a thing.

  The electrophotographic toner of the present invention will be described below.

(Dye dispersion method)
The electrophotographic toner of the present invention is obtained by directly dispersing a dye dispersion in a binder resin or mixing a colored fine particle dispersion, and further using a desired additive described later, a kneading / pulverizing method, a suspension polymerization method, It can be produced by other known methods such as an emulsion polymerization method, an emulsion dispersion granulation method, and an encapsulation method. Of these production methods, emulsion polymerization is preferred from the viewpoints of production cost and production stability, in consideration of the reduction in toner particle size associated with higher image quality. The emulsion polymerization method involves mixing the thermoplastic resin emulsion produced by emulsion polymerization with a dispersion of toner particle components, such as other dye solid dispersions, and agglomeration due to the repulsive force of the particle surface generated by pH adjustment and addition of an electrolyte. Toner particles are produced by slowly agglomerating while balancing the force, associating while controlling the particle size and particle size distribution, and simultaneously performing heating and stirring to control the fusion and shape between the fine particles.

  When directly dispersing the dye dispersion, it is possible to disperse using a commonly used roll grinder disperser, bead disperser, high-speed stir disperser, medium stirrer, etc. A similar method can be used. That is, it can also be obtained by dissolving (or dispersing) a dye in an organic solvent, emulsifying and dispersing in water, and then removing the organic solvent.

(Colored fine particles)
As one form of the electrophotographic toner of the present invention, at least colored fine particles can be dispersed in a thermoplastic resin. The colored fine particles are characterized by containing at least the metal complex compound represented by the general formula (1), and the dispersed particle diameter of the colored fine particles can be controlled by using a dispersion method such as a liquid drying method described later. It is. It is also preferable to further contain a resin having a composition different from that of the thermoplastic resin or a high-boiling solvent, and the dye is directly dispersed in a toner binder resin generally known as a toner using the above-mentioned dye, Alternatively, instead of dissolving, colored fine particles (including those in which a dye is simply dispersed) can be dispersed in a thermoplastic resin.

  Since the pigment in the colored fine particles dissolves in the resin at the molecular level, it becomes possible to eliminate components such as concealing particles that block light in the toner, and the transparency of each toner in a single color is improved. It is considered that transparency in the superimposed color is also improved. FIG. 1 schematically shows a cross section of an electrophotographic toner particle of the present invention in which colored fine particles are dispersed in a thermoplastic resin. As an example of a preferred form, the colored fine particles may be coated with an outer shell resin (shell) as shown in FIG. 2, and in this case, a resin and a thermoplastic resin (core) inside the colored fine particles (core) There are no restrictions on the combination of binder resins), the degree of freedom of materials is large, and the same manufacturing conditions are used if only the outer shell resin (shell) is the same for the four color toners (yellow, magenta, cyan, black). This makes it possible to manufacture with a large cost. In addition, since the dye that is the colorant does not migrate out of the colored fine particles (exposure to the surface of the colored fine particles), the dye sublimation or oil during heat fixing, which is generally regarded as a problem in toners using dyes. There is no concern about contamination.

(Preparation method of colored fine particles)
Next, an example of a method for producing colored fine particles, which is one of the preferred embodiments according to the present invention, will be described.

  The colored fine particles according to the present invention are obtained by, for example, dissolving (or dispersing) a dye (or dye and resin, a high boiling point organic solvent, an additive, etc.) in an organic solvent, and emulsifying and dispersing in water, and then removing the organic solvent. (It can be obtained by in-liquid drying method.) When a resin is further added and coated with an outer shell resin (shell), a monomer having a polymerizable unsaturated double bond is added to the colored fine particles to activate Colored fine particles having a core-shell structure can be obtained by carrying out emulsion polymerization in the presence of an agent and depositing on the core surface simultaneously with the polymerization. Alternatively, for example, an aqueous dispersion of resin fine particles is formed in advance by emulsion polymerization, an organic solvent solution in which a dye is dissolved is mixed in the aqueous dispersion of resin fine particles, and then the resin fine particles are impregnated with the dye, and then the coloring is performed. It can be obtained by various methods such as a method of forming a shell using fine particles as a core.

  The shell is preferably made of an organic resin, and as a method for forming the shell, there is a method in which a resin dissolved in an organic solvent is gradually dropped and the resin is adsorbed on the surface of the colored fine particle core simultaneously with the precipitation. After forming colored fine particles that form a core containing a dye and a resin, a monomer having a polymerizable unsaturated double bond is added, and emulsion polymerization is performed in the presence of an activator. A method of forming a shell is preferred.

  In addition, the dye may be formed by dispersing it in water using a surfactant or the like using a bead disperser, a high-speed agitation disperser, a medium type agitator, or the like.

(Normal surfactant)
In emulsification at the time of preparing colored fine particles, which is one of the preferred forms according to the present invention, a normal anionic emulsifier (surfactant) and / or a nonionic emulsifier (surfactant) may be used as necessary. it can.

  Examples of the normal nonionic emulsifier include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether, and sorbitan monolaurate. Sorbitan higher fatty acid esters such as sorbitan monostearate and sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene monolaurate, polyoxyethylene monostearate, etc. Higher fatty acid esters of glycerin such as polyoxyethylene higher fatty acid esters, oleic acid monoglyceride, stearic acid monoglyceride Class, polyoxyethylene - polyoxypropylene - and the like block copolymer.

  Examples of the usual anionic emulsifier include higher fatty acid salts such as sodium oleate, alkylaryl sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfates such as sodium lauryl sulfate, polyethoxyethylene lauryl ether sulfate. Polyoxyethylene alkyl ether sulfates such as sodium, polyoxyethylene alkyl aryl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate, sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate And alkylsulfosuccinic acid ester salts, and derivatives thereof.

(dye)
The dye used in the present invention will be described.

  In the present invention, generally known dyes can be used. In the present invention, the dye is preferably an oil-soluble dye. Oil-soluble dyes are usually dyes that are soluble in organic solvents that do not have water-soluble groups such as carboxylic acids and sulfonic acids and are insoluble in water. However, oil-soluble dyes are oil-soluble by salting water-soluble dyes with long-chain bases. The dye which shows is also included. For example, acid dyes, direct dyes, and salt-forming dyes of reactive dyes and long chain amines are known.

  Although not limited to the following, for example, Valifast Yellow 4120, Variast Yellow 3150, Varifast Yellow 3108, Varifast Yellow 2310N, Varifast R1 304, Valifast R1 304, Valifast R3 , BaliFast Blue 2610, Valifast Blue 2606, VariFast Blue 1603, Oil Yellow GG-S, Oil Yellow 3G, Oil Yellow 129, Oil Yellow 107, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105 Il Red RR, Oil Red OG, Oil Red 5B, Oil Pink 312, Oil Blue BOS, Oil Blue 613, Oil Blue 2N, Oil Black BY, Oil Black BS, Oil Black 860, Oil Black 5970Ol Black 5960 5905, Kayset Yellow SF-G, Kayset Yellow K-CL, Kayase Yellow GN, Kayase Yellow A-G, Kayset Yellow 2G, Kayset Red SF-4G, Kayase Red Kad SetK-4 -BR, Kayset Magenta 312, Kay set Blue K-FL, FS Yellow 1015, FS Magenta 1404, FS Cyan 1522, FS Blue 1504, C.I. I. Solvent Yellow 88, 83, 82, 79, 56, 29, 19, 16, 14, 04, 03, 02, 01, C.I. I. Solvent Red 84: 1, C.I. I. Solvent Red 84, 218, 132, 73, 72, 51, 43, 27, 24, 18, 01, C.I. I. Solvent Blue 70, 67, 44, 40, 35, 11, 02, 01, C.I. I. Solvent Black 43, 70, 34, 29, 27, 22, 7, 3, C.I. I. Solvent Violet 3, C.I. I. SolventGreen 3 and 7, Plast Yellow DY352, Plast Red 8375, MS Yellow HD-180 manufactured by Mitsui Chemicals, MS Red G, MS Magenta HM-1450H, MS Blue HM-1384, ES Red 3001, manufactured by Sumitomo Chemical Co., Ltd. , ES Red 3003, TS Red 305, ES Yellow 1001, ES Yellow 1002, TS Yellow 118, ES Orange 2001, ES Blue 6001, TS Turq Blue 618, Bayer's MACROL Yellow Yellow 6G, CeresBlu 75E , MACROLEX Red Vio let R and the like.

  Disperse dyes can be used as the oil-soluble dye, and are not limited to the following, but examples thereof include C.I. I. Disperse Yellow 5, 42, 54, 64, 79, 82, 83, 93, 99, 100, 119, 122, 124, 126, 160, 184: 1, 186, 198, 199, 204, 224 and 237; C . I. Disperse Orange 13, 29, 31: 1, 33, 49, 54, 55, 66, 73, 118, 119 and 163; C.I. I. Disperse Red 54, 60, 72, 73, 86, 88, 91, 92, 93, 111, 126, 127, 134, 135, 143, 145, 152, 153, 154, 159, 164, 167: 1, 177 , 181, 204, 206, 207, 221, 239, 240, 258, 277, 278, 283, 311, 323, 343, 348, 356 and 362; I. Disperse violet 33; C.I. I. Disperse Blue 56, 60, 73, 87, 113, 128, 143, 148, 154, 158, 165, 165: 1, 165: 2, 176, 183, 185, 197, 198, 201, 214, 224, 225 257, 266, 267, 287, 354, 358, 365 and 368 and C.I. I. Disperse Green 6: 1 and 9 etc. are mentioned.

  Other particularly preferable oil-soluble dyes include azomethine dyes and indoaniline dyes derived from couplers such as cyclic methylene compounds such as phenol, naphthols, pyrazolones and pyrazolotriazoles, and open-chain methylene compounds.

  Preferable examples of such dyes include, for example, JP-A-3-114892, JP-A-4-62092, JP-A-4-62094, JP-A-4-82896, JP-A-5-16545, JP-A-5-177958, and JP-A-5-301470. And dyes described in No. 1.

(Particle size)
The colored fine particles, which is one of the preferred forms in the present invention, preferably have a volume average particle diameter in the range of 10 nm to 1 μm. When the volume average particle diameter is 10 nm or less, the surface area per unit volume becomes very large. The effect of encapsulating the dye in the polymer of the colored fine particles is reduced, the stability of the colored fine particles is liable to deteriorate, and the storage stability is liable to deteriorate. On the other hand, when the particle size is larger than 1 μm, sedimentation is likely to occur during the production of the fine particle, and the stagnation stability is deteriorated. In addition, when the toner is used, the glossiness is deteriorated and the transparency is remarkably deteriorated. Therefore, the average particle diameter of the colored fine particles is preferably 10 to 1 μm, more preferably 10 to 500 nm, and still more preferably 10 to 100 nm.

  The volume average particle diameter can be determined using a dynamic light scattering method, a laser diffraction method, a centrifugal sedimentation method, an FFF method, an electrical detector method, etc. In the present invention, a Zetasizer manufactured by Malvern is used. Thus, it is preferable to obtain by the dynamic light scattering method.

(Dye content)
The colored fine particles according to the present invention preferably have a dye content in the range of 10 to 70% by mass. When the dye is contained in an amount of 10 to 70% by mass, a sufficient concentration can be obtained and the colorant can be protected by the resin. Since it is expressed and excellent in storage stability as a fine particle dispersion, it is possible to prevent an increase in particle size due to aggregation or the like.

(Metal-containing compound content)
The metal-containing compound represented by the general formula (1) may be used alone or in combination of two, but it is preferably 0.8 to 3 times mol, more preferably 1 with respect to the colorant. Although it depends on the dye used in combination, the light resistance is remarkably improved when the amount is more than 0.8 times mole, and the dispersion stability of the colored fine particles is improved when the amount is less than 3 times mole, This is advantageous when toner is used.

(toner)
In the electrophotographic toner of the present invention, a known charge control agent, offset preventive agent and the like can be used in addition to the above-mentioned thermoplastic resin and colored fine particles. The charge control agent is not particularly limited. As the negative charge control agent used in the color toner, a colorless, white, or light color charge control agent that does not adversely affect the color tone and translucency of the color toner can be used. For example, a zinc or chromium metal complex of a salicylic acid derivative , Calixarene compounds, organoboron compounds, fluorine-containing quaternary ammonium salt compounds and the like are preferably used. Examples of the salicylic acid metal complex include those described in JP-A No. 53-127726 and JP-A No. 62-145255, and examples of the calixarene compound include, for example, JP-A No. 2-201378. As the organic boron compound, those described in JP-A-2-221967 can be used, and as the organic boron compound, for example, those described in JP-A-3-1162 can be used. is there. When such a charge control agent is used, it is desirable to use 0.1 to 10 parts by mass, preferably 0.5 to 5.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin (binder resin).

  There are no particular restrictions on the anti-offset agent. For example, polyethylene wax, oxidized polyethylene wax, polypropylene wax, oxidized polypropylene wax, carnauba wax, sazol wax, rice wax, candelilla wax, jojoba oil wax, honey Wax wax or the like can be used. The added amount of such wax is 0.5 to 5 parts by mass, preferably 1 to 3 parts by mass with respect to 100 parts by mass of the thermoplastic resin (binder resin). This is because if the addition amount is less than 0.5 parts by mass, the effect of the addition is insufficient, and if it exceeds 5 parts by mass, the translucency and color reproducibility deteriorate.

  Moreover, in order to improve the preservability of a pigment | dye, the compound described and quoted on pages 10-13 of Unexamined-Japanese-Patent No. 8-29934 may be added as an image stabilizer, for example, the phenol type currently marketed, Examples include amine-based, sulfur-based, and phosphorus-based compounds. For the same purpose, for example, an organic ultraviolet absorbent or an inorganic ultraviolet absorbent may be added as an ultraviolet absorbent. Examples of organic ultraviolet absorbers include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole. Benzotriazole compounds such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, etc., phenyl salsylate, 4-t-butylphenyl salsylate, 2, Hydroxybenzoates such as 5-t-butyl-4-hydroxybenzoic acid n-hexadecyl ester, 2,4-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate System compounds and the like. Examples of inorganic ultraviolet absorbers include titanium oxide, zinc oxide, cerium oxide, iron oxide, and barium sulfate. Organic ultraviolet absorbers are preferred, and ultraviolet absorbers include 50% transmittance. The wavelength at 350 nm is preferably 350 to 420 nm, more preferably 360 nm to 400 nm. When the wavelength is lower than 350 nm, the ultraviolet blocking ability is weak, and when the wavelength is higher than 420 nm, the coloring becomes strong. Although there is no restriction | limiting in particular about addition amount, The range of 10-200 mass% is preferable with respect to a pigment | dye, and 50-150 mass% is more preferable.

(Thermoplastic Resin) Binder Resin As the thermoplastic resin contained in the electrophotographic toner of the present invention, a thermoplastic resin that has high adhesion to colored fine particles or copper complex compound fine particles, which is one of the preferred forms. Particularly preferred is a solvent-soluble one. Further, if the polymer precursor is soluble in a solvent, a curable resin that forms a three-dimensional structure can also be used. As the thermoplastic resin, those generally used as a binder resin for a toner are used without particular limitation. For example, styrene resins, acrylic resins such as alkyl acrylates and alkyl methacrylates, and styrene acrylic copolymer resins. Polyester resins, silicone resins, olefin resins, amide resins, or epoxy resins are preferably used. However, in order to improve transparency and color reproducibility of superimposed images, transparency and melting characteristics are high. Resins with low viscosity and high sharp melt properties are required. As the binder resin having such characteristics, styrene resins, acrylic resins, and polyester resins are suitable.

  The number average molecular weight (Mn) is 3000 to 6000, preferably 3500 to 5500 as the binder resin, and the ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2 to 6, preferably 2. It is desirable to use a resin having a glass transition point of 0.5 to 5.5, a glass transition point of 50 to 70 ° C, preferably 55 to 70 ° C, and a softening temperature of 90 to 110 ° C, preferably 90 to 105 ° C.

  When the number average molecular weight of the binder resin is smaller than 3000, the image portion is peeled off when a full-color solid image is folded, and image defect occurs (folding fixability deteriorates). And the fixing strength decreases. If Mw / Mn is less than 2, high temperature offset is likely to occur. If Mw / Mn is greater than 6, sharp melt characteristics at the time of fixing deteriorate, and the translucency of toner and color mixing at the time of full color image formation decrease. End up. Further, if the glass transition point is lower than 50 ° C., the heat resistance of the toner becomes insufficient, and toner aggregation tends to occur during storage. Color mixing at the time of image formation is reduced. Further, when the softening temperature is lower than 90 ° C., high temperature offset tends to occur. When the softening temperature is higher than 110 ° C., fixing strength, translucency, color mixing property, and gloss of a full color image are deteriorated.

  The electrophotographic toner of the present invention uses the above-described thermoplastic resin (binder resin), colored fine particles, and other desired additives (the fine particles may be mixed in several kinds or in each kind of fine particles). Well), kneading and pulverizing methods, suspension polymerization methods, emulsion polymerization methods, emulsion dispersion granulation methods, encapsulation methods, and other known methods. Among these production methods, the emulsion polymerization method is preferred from the viewpoints of production cost and production stability in consideration of the reduction in the toner particle size accompanying the increase in image quality.

  In the emulsion polymerization method, the thermoplastic resin emulsion produced by emulsion polymerization is mixed with a dispersion of toner particle components such as other colored fine particles, and the balance between the repulsive force of the particle surface produced by pH adjustment and the cohesive force due to the addition of an electrolyte. The toner particles are produced by slowly agglomerating while taking particles, and performing association while controlling the particle diameter and particle size distribution, and at the same time, fusing and shape control between the fine particles by heating and stirring. The toner particles for electrophotography of the present invention preferably have a volume average particle diameter of 4 to 10 μm, preferably 6 to 9 μm, from the viewpoint of high-definition image reproducibility.

  In the electrophotographic toner of the present invention, a post-treatment agent can be added and mixed from the viewpoint of imparting toner fluidity and improving cleaning properties, and is not particularly limited. Examples of such post-treatment agents include inorganic oxide fine particles such as silica fine particles, alumina fine particles, and titania fine particles, inorganic stearate compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, and strontium titanate and titanium. Inorganic titanate compound fine particles such as zinc oxide can be used, and it is possible to use single or different additives in combination. These fine particles are desirably used after being surface-treated with a silane coupling agent, a titanium coupling agent, a higher fatty acid, silicone oil, etc. from the viewpoints of environmental stability and heat-resistant storage stability. On the other hand, it is desirable to use 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass.

  The toner for electrophotography of the present invention can be used as a two-component developing toner used by mixing with a carrier, or as a one-component developing toner not using a carrier.

  As the carrier used in combination with the electrophotographic toner of the present invention, conventionally known carriers can be used as a carrier for two-component development, for example, a carrier made of magnetic particles such as iron or ferrite, A resin-coated carrier obtained by coating such magnetic particles with a resin, or a binder-type carrier obtained by dispersing magnetic fine powder in a binder resin can be used. Among these carriers, a silicone resin, a copolymer resin (graft resin) of an organopolysiloxane and a vinyl monomer, or a resin-coated carrier using a polyester resin can be used as a coating resin, such as toner spent. From the viewpoint, a carrier coated with a resin obtained by reacting an isocyanate with a copolymer resin of an organopolysiloxane and a vinyl monomer is particularly preferable from the viewpoint of durability, environmental stability, and spent resistance. . As the vinyl monomer, it is necessary to use a monomer having a substituent such as a hydroxyl group reactive with isocyanate. In addition, it is preferable to use a carrier having a volume average particle diameter of 20 to 100 μm, preferably 20 to 60 μm from the viewpoint of ensuring high image quality and preventing carrier fogging.

(Image forming method)
Next, an image forming method using the electrophotographic toner of the present invention will be described.

  In the present invention, the image forming method is not particularly limited. For example, a method of forming a plurality of images on a photosensitive member and transferring them in a batch, a method of sequentially transferring images formed on the photosensitive member to a transfer belt, etc. are not particularly limited, but more preferably a plurality of images on the photosensitive member. This image is formed and transferred at once.

  In this method, the photosensitive member is uniformly charged and exposed in accordance with the first image, and then the first development is performed to form a first toner image on the photosensitive member. Next, the photoconductor on which the first image is formed is uniformly charged, and exposure according to the second image is given, and the second development is performed to form a second toner image on the photoconductor. Further, the photoconductor on which the first and second images are formed is uniformly charged, exposure according to the third image is performed, the third development is performed, and a third toner image is formed on the photoconductor. . Further, the photosensitive member on which the first, second, and third images are formed is uniformly charged, exposed according to the fourth image, developed for the fourth time, and the fourth toner image on the photosensitive member. To form.

  For example, a full color toner image is formed on the photosensitive member by developing the first time with yellow, the second time with magenta, the third time with cyan, and the fourth time with black toner. Thereafter, the image formed on the photoreceptor is collectively transferred to an image support such as paper, and further fixed on the image support to form an image.

  In this method, the images formed on the photoconductor are collectively transferred to paper or the like to form an image. Therefore, unlike the so-called intermediate transfer method, the number of times of transfer that disturbs the image is one time. In fact, the image quality can be improved.

  Non-contact development is preferable because a plurality of developments are necessary as a method of developing on the photoreceptor. In addition, a method in which an alternating electric field is applied during development is also a preferable method.

  As described above, the non-contact development method is preferable as the development method for forming a superimposed color image on the image forming body and transferring the images collectively.

  The volume average particle size of the carrier that can be used as the two-component developer is 15 to 100 μm, more preferably 25 to 60 μm. The volume average particle diameter of the carrier can be typically measured by a laser diffraction particle size distribution measuring apparatus “HELOS” (manufactured by SYMPATEC) equipped with a wet disperser.

  The carrier is preferably further coated with a resin, or a so-called resin-dispersed carrier in which magnetic particles are dispersed in the resin. The resin composition for coating is not particularly limited, and for example, olefin resin, styrene resin, styrene / acrylic resin, silicone resin, ester resin, or fluorine-containing polymer resin is used. The resin for constituting the resin-dispersed carrier is not particularly limited, and known resins can be used. For example, styrene / acrylic resin, polyester resin, fluorine resin, phenol resin, etc. are used. Can do.

  A preferred fixing method used in the present invention is a so-called contact heating method. In particular, typical examples of the contact heating method include a heat roll fixing method and a pressure heating fixing method in which fixing is performed by a rotating pressure member including a fixedly arranged heating body.

(image)
In image formation in which development, transfer, and fixing are performed using the electrophotographic toner of the present invention, the state from the transfer to the fixing is that the electrophotographic toner of the present invention transferred onto the transfer material is fixed after fixing. However, the colored fine particles are not disintegrated and are attached to the surface of the paper in a dispersed state in the toner particles.

  In the present invention, since the colored fine particles are dispersed in the toner particles as described above, the toner particles contain a high concentration of the dye, but the dye is not released to the surface of the toner particles (does not migrate). This is a problem of the toner in which the dye obtained by dispersing or dissolving the dye in the thermoplastic resin (toner binder resin) as it is conventionally is exposed on the surface of the toner particles. 2) Large difference in charge amount between high temperature and high humidity and low temperature and low humidity (environment-dependent) 3) Kind of colorant For example, each pigment of cyan, magenta, yellow and black is used for full color image recording. When the toner is used, it is possible to wipe away the variation in charge amount of each color toner. In addition, there is no migration of the dye, which is a colorant, outside the colored fine particles (exposure to the surface of the colored fine particles) during heat fixing to the transfer material. There will be no dye sublimation or oil contamination.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these embodiments. In the examples, “part” or “%” is based on mass unless otherwise specified.

Example 1
A pulverized toner and a polymerized toner were prepared by using the following pulverized toner manufacturing method and polymerized toner manufacturing method (two types).

<Preparation method of pulverized color toner>
95 parts of a polyester resin, a mixture of colorants shown in Table 1 and the metal-containing compound of the present invention (1 / 1.03 molar ratio) were added in the following number of parts, polypropylene resin (Biscol 550P: manufactured by Sanyo Chemical Co., Ltd.) 2.5 Were mixed, ground meat, pulverized, and classified to obtain a powder having an average particle size of 8.7 μm. Further, 100 parts of this powder and 1.0 part of silica fine particles R805 (manufactured by Nippon Aerosil Co., Ltd., particle size 12 nm, hydrophobicity 60) were mixed with a Henschel mixer to obtain a pulverized color toner.

Yellow 4.5 parts Magenta 2 parts Cyan 2 parts <Preparation of color toner by polymerization method>
<Preparation of colorant dispersion>
20 g of a mixture of the colorant shown in Table 1 and the metal-containing compound of the present invention (1 / 1.03 molar ratio) was added to a solution obtained by dissolving 5 g of sodium dodecyl sulfate in 200 ml of pure water, and stirring and ultrasonic waves were added. By applying, an aqueous dispersion of a magenta colorant was prepared. Further, an emulsified dispersion was prepared by emulsifying low molecular weight polypropylene (number average molecular weight 3300) in water so as to have a solid concentration of 31% with a surfactant while heating.

<Preparation of color toner>
62 g of low molecular weight polypropylene emulsified dispersion is mixed with the above colorant dispersion, and 223 g of styrene, 39 g of butyl acrylate, 11 g of methacrylic acid, 5.5 g of t-dodecyl mercaptan as a chain transfer agent, and 2,000 ml of degassed pure water. Then, the emulsion polymerization was carried out by maintaining at 70 ° C. for 3 hours while stirring under a nitrogen stream.

  Sodium hydroxide was added to 1,000 ml of the resulting dispersion of colorant-containing resin fine particles to adjust the pH to 7.0, 270 ml of a 2.7 mol / L aqueous potassium chloride solution was added, and 160 ml of i-propyl alcohol and 9.0 g of polyoxyethylene octyl phenyl 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 by stirring for 6 hours while maintaining at 75 ° C. The obtained reaction liquid was filtered and washed with water, and further dried and crushed to obtain colored particles.

  The colored particles and 1.0 part of silica fine particles R805 (supra) were mixed with a Henschel mixer to obtain a polymerization method color toner.

<Manufacture of carriers>
When an external magnetic field of 40 g of styrene / methyl methacrylate (4/6) copolymer fine particles (average particle size 80 nm), Cu—Zn ferrite particles (specific gravity 5.0, mass average particle size 45 μm, 1,000 oersted) is applied. Is charged into a high-speed agitating mixer, mixed at 30 ° C. for 15 minutes, then set to 105 ° C., mechanical impact force is repeatedly applied for 30 minutes, and the carrier is cooled and cooled. Got.

<Production of developer for live-action test>
The carrier 214g and each toner 16g were mixed for 20 minutes using a V-type mixer to produce developers 1 to 28 for a live-action test. The resulting developer composition is shown in Table 1.

<Image formation>
Using a color copying machine (KL-2010: manufactured by Konica Minolta Co., Ltd.) as an image forming apparatus, actual image evaluation was performed. As the fixing device, a commonly used heat roll fixing type was used. Specifically, the surface of a cored bar made of an aluminum alloy with a built-in heater at the center (inner diameter = 40 mm, wall thickness = 1.0 mm, overall width = 310 mm) is coated with tetrafluoroethylene-perfluoroalkyl vinyl ether. A heated roller is formed by coating with a 120 μm thick tube of coalescence (PFA), and the surface of a cylindrical core made of iron (inner diameter = 40 mm, wall thickness = 2.0 mm) is made of sponge silicone rubber (Asker C A pressure roller was formed by coating with a hardness of 48 and a thickness of 2 mm, and the heating roller and the pressure roller were brought into contact with a load of 150 N to form a 5.8 mm wide nip.

  Using this fixing device, the printing linear velocity was set to 440 mm / sec. As a cleaning mechanism for the fixing device, a web type supply system impregnated with polydiphenyl silicone (having a viscosity at 20 ° C. of 10 Pa · s) was used. The fixing temperature was controlled by the surface temperature of the heating roller (set temperature 176 ° C.). The application amount of silicone oil was 0.1 mg / A4 size.

<Evaluation>
Reflective images (images on paper) were respectively produced on paper using the above-described image forming apparatus with the toner set using the color toner of the present invention, and evaluated by the following methods. The toner adhesion amount was evaluated in the range of 0.7 ± 0.05 (mg / cm ² ).

(Hue evaluation)
The hue was visually evaluated by 10 subjects and evaluated with a maximum of 10 points. The average score of 10 people was A to 10-9, the average score of 10 to 9 was B, the average score of 10 to 8 was C, and less than 7 was D.

<Light resistance>
After measuring the image density D ₀ immediately after recording, a 6-day exposure test was performed using “Xenon Long Life Weather Meter” (Xenon Arc Lamp, 70,000 lux, 24.0 ° C.) manufactured by Suga Test Instruments Co., Ltd. The image density D was measured again, and the dye residual ratio was calculated and evaluated from the difference in image density before and after the xenon light irradiation.
A: Dye residual ratio 80% or more B: Dye residual ratio 70% to less than 80% C: Dye residual ratio 60% to less than 70% D: Dye residual ratio less than 60% A and B are at a level that does not cause any practical problems.

(Chargeability humidity dependence)
Regarding the humidity dependency of the charging property, the magenta developing device is set in a single driving device for driving the magenta developing device of a commercially available digital color copying machine (multifunction machine) bizhub c352 (manufactured by Konica Minolta Business Technologies), and the toner of the present invention The developer was set so that the toner concentration mixed with the carrier was 6%.

  Two developing units left at 20 ° C. and 50% for 72 hours were transferred to 1) 33 ° C. and 80% RH environment and left for 2 hours. Furthermore, 2) it was transferred to an environment of 10 ° C. and 12% RH and left for 2 hours.

The developer in 1) and 2) were driven for 30 seconds and 1200 seconds, 5 g of each developer was sampled, and the charge amount of the toner was measured by a known blow-off method.
A: 30-second value, 1200-second value, 2) environmental value and 1) environmental value are less than 3 micro C / g. B: 30-second value, 1200-second value, 2) environmental value and 1 ) Environmental value of 3 micro C / g or more, less than 5 micro C: 30 second value and 1200 second value, 2) environmental value and 1) environmental value of 7 micro C / g or more.

(Charging speed)
1000 sheets were printed in a print mode in which the pixel rate was 75%, and the toner consumption and replenishment amount were remarkably large, and toner spillage in the machine and image blur of the printed image were visually evaluated.
A: No toner spillage due to poor charging, no blurring of image B: No toner spillage due to poor charging, but slight blurring occurred at the trailing edge of the print, but no problem in practical use C: Toner spillage due to poor charging, image Scratch occurs and is a practical problem.

(Blank evaluation)
Developers listed in Table 1 are set in a full-color copying machine (CF-3102: two-component development method), and each CW ratio is 5% (red (R), green (G), blue (B), black (Bk) ), Cyan (C), magenta (M), yellow (Y) (total 35%) images were printed 1000 sheets. The image samples obtained after storing the machine for 24 hours in a laboratory environment (23 ° C., 55%) and a high temperature and high humidity (HH) environment (30 ° C., 85%), which are severe conditions, are then used. (Transferability) was evaluated. When the evaluation environment is high temperature and high humidity, the cohesive force between the toners becomes strong, and the charge amount decreases, so that the hollowing out performance deteriorates.
A: No void occurred on the image.
B: Slight omissions occurred in the image, but did not reach the level of image loss, and there was no problem in practical use.
C: There were many problems in practical use because a large number of voids occurred in the image and some image defects occurred.

  When an image was printed using the developer of the comparative example, the heat roll was confirmed to be smudged by a hollow, but all the images printed using the developer of the present invention were confirmed to be smudged on the heat roll. There wasn't.

  As can be seen from Table 1, by using the color toner of the present invention, since the light resistance is good, it is possible to provide an image showing good storage stability over a long period of time, and further, the water resistance of the toner is improved. The charging property was stabilized, and the void in the image could be improved.

Claims (5)

An electrophotographic toner comprising at least one metal-containing compound represented by the following general formula (1):

[Wherein, M represents a divalent metal ion, R ₁ represents an aryl group, an alkenyl group, an alkynyl group or a 6-membered aromatic heterocyclic group, and R ₂ represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. Group, aryl group, heterocyclic group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, halogen atom or cyano group, R ₃ represents a branched alkyl group , An alkenyl group, an alkynyl group, or a group containing a ring structure. ] The electrophotographic toner according to claim 1, wherein the group represented by R ₁ in the general formula (1) is substituted with at least one electron-withdrawing group. The electrophotographic toner according to claim 1, wherein M in the general formula (1) is Cu ²⁺ . The toner for electrophotography according to claim 1, wherein R ₃ in the general formula (1) is a group containing a ring structure. The metal compound which can be used for the toner for electrophotography of any one of Claims 1-4 is represented by following General formula (2), The metal containing compound characterized by the above-mentioned.

[Wherein, R _a1 represents an aryl group, an alkenyl group, an alkynyl group, or a 6-membered aromatic heterocyclic group, and R _a2 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, or an alkoxy group. A carbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a halogen atom or a cyano group is represented, and R _a3 represents a group containing a ring structure. ]