JP2007298642A - Electrophotographic toner and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic toner materializing good coloring without making an issue of dispersibility in a thermoplastic resin, excellent in transparency and color reproducibility, excellent also in heat resistance, charging property and offset resistance, and using no highly harmful metal. <P>SOLUTION: In the electrophotographic toner, a dye represented by formula (1) and a copper compound represented by the formula (2): Cu<SP>2+</SP>(Z<SP>1</SP>)<SB>p</SB>(Z<SP>2</SP>)<SB>q</SB>W<SP>1</SP>are dispersed in a thermoplastic resin. An image forming method using the electrophotographic toner is also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an electrophotographic toner and an image forming method using the electrophotographic toner.

  In recent years, the dispersed light is exposed on a photoconductor to form an electrostatic latent image of an original, which is developed with each color toner to obtain a colored copy image, or each color copy image is superimposed. A color copying method for obtaining a full-color copy image has been put into practical use, and color toners such as yellow, magenta, and cyan in which pigments and / or dyes of various colors are dispersed in a binder resin are manufactured as color toners used for this. Yes.

  The above-mentioned electrophotographic method generally forms an image by the following steps.

  First, an electrostatic latent image is formed on the photoconductor by irradiating light information corresponding to image information by various methods onto the photoconductor composed of a photoconductive substance. Next, the electrostatic latent image formed on the photosensitive member is developed as a toner image with charged toner, and the toner image is transferred to an image recording medium (for example, plain paper or an intermediate transfer member). Then, the image is fixed on plain paper using a heat fixing device.

  In the color image forming method using the above-described electrophotographic method, the electrostatic latent image formed on the photoconductor corresponds to image information separated into yellow, magenta, cyan, and black colors, The toner of the same color as each image information is developed. A color image is formed by repeating this development process four times for each color.

  Conventionally known organic pigments and dyes have been used as colorants used in electrophotographic toners, but each has various drawbacks.

  For example, organic pigments are generally superior in heat resistance and light resistance compared to dyes. However, since they exist in the form of particles dispersed in the toner, the hiding power is increased and the transparency is lowered. Further, since the dispersibility of the pigment is generally poor, the transparency is impaired, the saturation is lowered, and the color reproducibility of the image is hindered. In addition, in order to make it possible to visually confirm the color of the toner in the lowermost layer, the lowermost toner in the color-superposed toner is not hidden by the upper layer, and is fixed. In addition, the transparency of the toner is required, and in order to maintain the color reproducibility of the original, the dispersibility of the colorant and the coloring power are required.

  As a method for eliminating the disadvantages of the pigment, for example, by using a flushing method as a pigment dispersion method, the transparency of the pigment is improved by achieving a submicron order pigment dispersion diameter by primary particles without aggregated secondary particles. Means and means for improving the charging property, fixing property and image uniformity by coating pigment particles with a binder resin and an outer shell resin have been proposed (for example, see Patent Documents 1 and 2).

  However, even in the case of outputting with the toner proposed in these cases, it is still difficult to obtain sufficient transparency in the case of the toner using pigment.

  In color image forming apparatuses, in principle, all color reproduction can be performed by subtractive color mixing using the three primary colors of yellow, magenta, and cyan. In reality, however, the spectral characteristics when a pigment is dispersed in a thermoplastic resin. The range of color reproducibility and saturation are reduced by the color mixing characteristics when toners of different colors are superimposed on each other, so there are still many problems remaining to faithfully reproduce the color of the document. Yes.

  On the other hand, a toner using a dye, a toner obtained by mixing a dye and a pigment, and the like are disclosed (for example, see Patent Documents 3 and 4).

  Generally, in a toner using a dye, the dye is present in a dissolved state in the binder resin of the toner, so that the transparency and saturation are excellent, but the light resistance and heat resistance are larger than those of the pigment. It has the disadvantage of being inferior. Concerning heat resistance, in addition to the decrease in density due to the decomposition of the dye, when the toner image is fixed with a heat roller, the dye tends to sublime and cause contamination inside the machine, and the dye dissolves in the silicone oil used for fixing. In the end, however, there is a problem of causing an offset phenomenon by fusing to a heating roll.

  As a proposal to eliminate these disadvantages of dyes, for example, a means for achieving both light fastness, sublimation and color reproducibility by using organic dye chelate dyes and phthalocyanine dyes having a trimethine chain as cyan toner is proposed. (For example, see Patent Documents 5, 6, and 7). Further, an example in which a chelate dye of an organic dye having a trimethine chain is contained in a recording layer of an optical recording medium has been presented, but there is no description used for a toner (for example, Patent Document 8).

However, even in the case of outputting with the toners proposed in these cases, it is still difficult to obtain sufficient light resistance in the case of toners using dyes, and some of the metals used in chelating dyes are safe. There are many problems (nickel and cobalt), and development of a toner that satisfies these conditions is desired.
Japanese Patent Laid-Open No. 9-26673 JP-A-11-160914 JP-A-5-11504 JP-A-5-34980 Japanese Patent Laid-Open No. 10-20559 JP 2001-342364 A JP 2005-220253 A Japanese Patent Laid-Open No. 10-86517

  The object of the present invention has been made to solve the above-mentioned problems, and enables satisfactory coloring without causing dispersibility in a thermoplastic resin as a problem. Moreover, transparency and color reproducibility are achieved. To provide an electrophotographic toner excellent in heat resistance, chargeability, and offset resistance, and to provide an electrophotographic toner that does not use a highly harmful metal and an image forming method using the electrophotographic toner. is there.

  The above object of the present invention can be achieved by the following configuration.

  1. An electrophotographic toner comprising a thermoplastic resin in which a dye represented by the following general formula (1) and a copper compound represented by the general formula (2) are dispersed.

[Wherein R ¹ , R ² and R ³ each represent a hydrogen atom or a substituent, and X ¹ is an atom necessary for forming a 5-membered or 6-membered heterocyclic ring containing at least one nitrogen atom. Represents a group, may form a condensed ring, and may have a substituent. Y ¹ represents an aromatic hydrocarbon ring, a 5-membered or 6-membered heterocyclic ring, may form a condensed ring, and may have a substituent. R ⁴ represents an atomic group capable of forming at least a bidentate coordination bond with the metal ion and the nitrogen atom of X ¹ . ]
Formula (2) Cu ²⁺ (Z ¹ ) p (Z ² ) q · W ¹
[Wherein, Z ¹ and Z ² each independently represent a monodentate or bidentate ligand, and may be the same or different, and Z ¹ and Z ² may be linked. p and q represent the integer of 0-2. W ¹ represents a counter ion when a counter ion is required to neutralize the charge. ]
2. In the above general formula (1), at least one of R ¹ , R ² and R ³ is an electron withdrawing group having a Hammett substituent constant (σp) of 0.1 or more and 0.9 or less. The toner for electrophotography as described.

3. 3. The electrophotographic toner according to 1 or 2, wherein X ¹ in the general formula (1) is a group represented by the following general formula (3) or (4).

[Wherein, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ each independently represents a hydrogen atom or a substituent, and at least one of R ¹⁰ , R ¹¹ is a metal ion and nitrogen of the general formula (3) R ¹³ represents an atomic group capable of forming at least a bidentate coordination bond with the atom, R ¹³ represents an atomic group capable of forming at least a bidentate coordination bond with the nitrogen atom of the general formula (4), and * It represents a binding site with the carbon atom to which X ^{1 of the} trimethine dye represented by the general formula (1) is bonded. ]
4). 3. The electrophotographic toner according to 1 or 2, wherein X ¹ in the general formula (1) is a group represented by the following general formula (5) or (6).

[Wherein, R ¹⁵ and R ¹⁷ each independently represents a hydrogen atom or a substituent, and R ¹⁶ represents an atomic group capable of forming at least a bidentate coordination bond with the nitrogen atom of the general formula (5); R ¹⁸ represents an atomic group capable of forming at least a bidentate coordination bond together with the metal ion and the nitrogen atom of the general formula (6), and * represents the trimethine dye X ¹ represented by the general formula (1). Represents the bonding site with the bonded carbon atom. ]
5). 3. The electrophotographic toner according to 1 or 2, wherein X ¹ in the general formula (1) is a group represented by the following general formula (7) or (8).

[Wherein, R ¹⁹ , R ²⁰ , R ²² , R ²³ , R ²⁴ each independently represents a hydrogen atom or a substituent, and R ²¹ represents at least a bidentate together with a metal ion and a nitrogen atom of the general formula (7). Represents a group of atoms capable of forming a coordination bond, and at least one of R ²³ and R ²⁴ represents an atomic group capable of forming at least a bidentate coordination bond with the nitrogen atom of the general formula (8); It represents a binding site with the carbon atom to which X ^{1 of the} trimethine dye represented by the general formula (1) is bonded. ]
6). The toner for electrophotography according to any one of the 1 to 5, characterized in that the general formula (1) in R ⁴ is represented by any one of the following general formula (9) or (10).

[In the formula, Z ³ represents an atomic group that forms a 5- or 6-membered nitrogen-containing aromatic heterocycle with a nitrogen atom, R ³¹ represents a hydrogen atom or a substituent, and L ¹ has 1 or 2 carbon atoms. Q ¹ represents a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, an alkylsulfonylamino group, or an arylsulfonylamino group. ]
7). In any one of 1 to 6 above, at least one of the ligands (Z ¹ or Z ² ) of the copper compound represented by the general formula (2) is the following general formula (11): The toner for electrophotography as described.

(In the formula, E ¹ and E ² represent an electron-withdrawing group having a Hammett substituent constant (σp) of 0.1 to 0.9, and R represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryl group. Represents an oxy group or an amino group and may have a substituent.)
8). A dispersion obtained by emulsifying and dispersing the dye represented by the general formula (1) and the copper compound represented by the general formula (2) in water and a thermoplastic resin are dispersed. The electrophotographic toner according to any one of 1 to 7 above.

  9. The colored fine particles obtained by emulsifying and dispersing in water the dye medium resin having a composition different from the dye represented by the general formula (1), the copper compound represented by the general formula (2) and the thermoplastic resin are thermoplastic. 8. The electrophotographic toner according to any one of 1 to 7, wherein the toner is dispersed with a resin.

  10. 10. The electrophotographic toner as described in 9 above, wherein the colored fine particles comprise a core comprising a resin and a dye, and an outer shell resin (shell) covering the core.

  11. In an image forming method including at least a step of developing an electrostatic charge image formed on an electrostatic image bearing member with toner, and a step of transferring a toner image formed by development onto a transfer material, An image forming method using the electrophotographic toner according to any one of the above.

  The electrophotographic toner of the present invention and the image forming method using the electrophotographic toner enable good coloring without causing dispersibility in the thermoplastic resin as a problem, and also provide transparency and color reproducibility. An electrophotographic toner excellent in heat resistance, chargeability and offset resistance and an image forming method using the electrophotographic toner were obtained. Moreover, it had an excellent effect without using highly harmful metals.

  The present invention will be described in more detail. The electrophotographic toner of the present invention (hereinafter also simply referred to as toner) is obtained by dispersing a dye having a specific structure and a copper compound having a specific structure in a thermoplastic resin (hereinafter also referred to as a binder resin). Further, the dispersion is performed by emulsification dispersion in water.

  The toner for electrophotography of the present invention comprises at least colored fine particles dispersed in a thermoplastic resin. The colored fine particles contain a resin having a composition different from that of the thermoplastic resin, a dye having a specific structure, and a copper compound in water. It is characterized by being obtained by emulsifying and dispersing, and is different from directly dispersing or dissolving a dye in a toner binder resin generally known as a toner using a dye.

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin having a composition different from that of the thermoplastic resin and a dye having a specific structure represented by the general formulas (1) to (11) and It has been found that a color toner in which colored fine particles containing a copper compound are dispersed in a thermoplastic resin exhibits excellent hue and image fastness.

[Dye having a specific structure]
First, the dye capable of chelating with the metal represented by the general formula (1) will be described. In the general formula (1), R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a substituent, and examples of the substituent include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (for example, vinyl group, Allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), heteroaryl group (eg, furyl group, thienyl group, pyridyl group, pyridadyl group, pyrimidyl group) Group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzimid Zolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy) Group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.) , Alkylthio groups (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio groups (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio groups (eg, For example, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, Phenyloxycarbonyl group, naphthyloxycarbonyl 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.), acyl group (for example, aceto Group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group ( For example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonyl) Amino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcal Nylamino group, dodecylcarbonylamino group, trifluoromethylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl 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, phenylurea Raid group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, Naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (eg, 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, fluorine atom, chlorine atom, bromine atom, etc.) ) And the like.

Preferred substituents for R ^{1 to} R ³ are hydrogen atom, halogen atom, alkyl group, halogenated alkyl group, phenyl group, alkoxycarbonyl group, carbamoyl group, cyano group, carbonyl group, alkylsulfonyl group, alkylthio group, amino group. Etc. Of these, at least one of R ^{1 to} R ³ is preferably an electron-withdrawing group having a Hammett substituent constant (σp) of 0.1 or more and 0.9 or less.

  Here, a substituent having a Hammett substituent constant (σp) of 0.10 or more and 0.90 or less will be described.

  As the value of Hammett's substituent constant σp, 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)).

  Examples of the substituent or atom having a value of σp of 0.10 or more include a chlorine atom, a bromine atom, an iodine atom, a carboxyl group, a cyano group, a nitro group, and 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), carbamoyl groups (eg carbamoyl, methylcarbamoyl, phenylcarbamoyl, 2-chloro-phenylcarbamoyl), alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, Phenylmethylcarbonyl), substituted aromatic groups (eg pentachlorophenyl, pentafluorophenyl, 2,4-dimethanesulfonylphenyl, 2-trifluoromethylphenyl), heterocyclic residues (eg 2-benzoxazolyl, 2- Benzthiazolyl, 1-phenyl-2-benzimidazolyl, 1-tetrazolyl), azo group (eg phenylazo), ditrifluoromethylamino group, trifluoromethoxy group, alkylsulfonyloxy group (eg methanesulfonyloxy), acyloxy group (eg acetyl) Oxy, benzoyloxy), arylsulfonyloxy groups (for example, benzenesulfonyloxy), phosphoryl groups (for example, dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl groups (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl) and the like.

  In addition, as a substituent having a value of σp of 0.35 or more, 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), carbamoyl groups (eg, carbamoyl, methylcarbamoyl, phenylcarbamoyl, 2-chloro) -Phenylcarbamoyl), alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, diphenylmethylcarbonyl), fluorine or sulfonyl group substituted aromatic group (for example, pentafluorophenyl, 2,4-dimethanesulfonyl group) Nyl), heterocyclic residues (eg 1-tetrazolyl), azo groups (eg phenylazo), alkylsulfonyloxy groups (eg methanesulfonyloxy), phosphoryl groups (eg dimethoxyphosphoryl, diphenylphosphoryl), sulfamoyl groups, etc. Is mentioned.

  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.

Preferred examples of the electron withdrawing group for R ¹ , R ² and R ³ include a halogen atom, a halogen-substituted alkyl group (particularly a fluorine-substituted alkyl group), a cyano group, an alkoxycarbonyl group, an alkylsulfonyl group, and a nitro group.

In the general formula (1), X ¹ represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring containing at least one nitrogen atom. Specifically, (1) is preferably a coupler residue having an active hydrogen capable of forming a dye by a coupling reaction with p-phenylenediamine, and examples of the coupler residue include 5-pyrazolone, 5- Pyrazoloone, imidazole, pyrazolopyrrole, pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazole, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolone, isoxazolone, indandione, pyrazolidinedione, oxazolidine Examples include dione, hydroxypyridone, and pyrazolopyridone.

X ¹ may have a substituent, and examples of the substituent include the same groups as those described above for R ^{1 to} R ³ . Further, a condensed ring may be formed by the substituent.

R ⁴ represents an atomic group capable of forming at least a bidentate coordination bond with the metal ion and the nitrogen atom of X ¹ . A group of atoms capable of forming a coordination bond represents a substituent containing an atom having an unshared electron pair, specifically a heterocyclic group, a hydroxy group, a carbonyl group, an oxycarbonyl group, a carbamoyl group, an alkoxy group. , Heterocyclic oxy group, carbonyloxy group, urethane group, sulfonyloxy group, amino group, imino group, sulfonylamino group, sulfamoylamino group, acylamino group, ureido group, sulfonyl group, sulfamoyl group, alkylthio group, arylthio group And a heterocyclic thio group.

R ⁴ is preferably a group represented by the general formula (9) or (10).

In the general formula (9), Z ³ represents an atomic group that forms a 5-membered or 6-membered nitrogen-containing aromatic heterocycle together with a nitrogen atom. Specific examples include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, a thiazole ring, an isothiazole ring, an oxazole ring, an isoxazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, and a triazine ring. . Of these, a pyrazole ring, a pyridine ring, and a pyrazine ring are preferable. These nitrogen-containing aromatic heterocycles may have a substituent, and examples of the substituent include the same groups as the substituents represented by R ^{1 to} R ⁴ described above. Further, it may have a condensed ring.

R ³¹ represents a hydrogen atom or a substituent, and examples of the substituent include the same groups as the substituents represented by R ^{1 to} R ³ described above. Of these, a hydrogen atom, a halogen atom, an alkyl group, and an alkoxy group are preferable.

In the general formula (10), Q ¹ represents a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, an alkylsulfonylamino group, or an arylsulfonylamino group, preferably a hydroxyl group, an alkoxy group, or an alkylsulfonylamino group.

Examples of the linking group having 1 or 2 carbon atoms or a part of the ring structure represented by L ¹ include, for example, a substituted or unsubstituted methylene group, ethylene group, ethyne group, or a group represented by the following general formula (12). Can be mentioned.

In the general formula (12), Z ⁴ represents a 5-membered or 6-membered aromatic ring or heterocyclic ring and may have a substituent, and ** represents the carbon atom of X ^{1 in} the general formula (1). And *** to Q ¹ with ***.

L ¹ is preferably a methylene group, and the ring represented by Z ⁴ in the general formula (12) is preferably a benzene ring or a pyridine ring. The ring structure may have a substituent, and preferably includes a halogen atom, an alkoxy group, an amino group, an acylamino group, a sulfonylamino group, a ureido group, and the like, more preferably a halogen atom, An alkoxy group, an amino group, and an acylamino group are mentioned.

In the general formula (1), the substituent represented by X ¹ is more preferably a group represented by the above general formulas (3) to (8).

In general formula (3), (4), R < ¹⁰ > -R < ¹² >, R < ¹⁴ > represents a hydrogen atom or a substituent each independently. Examples of the substituent include the same groups as the substituents represented by R ^{1 to} R ³ described above, and R ^{10 to} R ¹² and R ¹⁴ include a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, It is preferably a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a sulfamoyl group, an alkylsulfonyl group or an arylsulfonyl group, more preferably an aryl group, a heterocyclic group, a carbamoyl group, an alkoxycarbonyl group, a cyano group. It is. * Represents a binding site with the carbon atom to which X ^{1 of the} trimethine dye represented by the general formula (1) is bonded.

At least one of R ¹⁰ and R ¹¹ represents an atomic group capable of forming at least a bidentate coordination bond with the metal ion and the nitrogen atom of the general formula (3), and the atomic group is preferably the same as R ⁴ Groups. More preferably, both R ¹⁰ and R ^{11 have} the same meaning as R ⁴ .

R ¹³ represents an atomic group capable of forming at least a bidentate coordination bond together with the metal ion and the nitrogen atom of the general formula (4), and preferably has the same meaning as R ⁴ .

In the general formulas (5) and (6), R ¹⁵ and R ¹⁷ each independently represents a hydrogen atom or a substituent. Examples of the substituent include the same groups as the substituents represented by R ^{1 to} R ⁴ described above, and R ¹⁵ and R ¹⁷ include a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, Acylamino group, alkylsulfonylamino group, arylsulfonylamino group, amino group, alkylthio group, arylthio group, alkoxy group, aryloxy group, ureido group, alkoxycarbonylamino group, carbamoyl group, carboxyl group or alkoxycarbonyl group Preferred are an alkyl group, a carboxyl group, an alkoxyl group, and a carbamoyl group, and more preferred are an alkyl group (particularly a methyl group, tert-butyl group, trifluoromethyl group), a carbamoyl group, and an alkoxycarbonyl group. * Has the same meaning as * in General Formulas (3) and (4).

R ¹⁶ represents an atomic group capable of forming at least a bidentate coordination bond together with the metal ion and the nitrogen atom of the general formula (5), and preferably has the same meaning as R ⁴ .

R ¹⁸ represents an atomic group capable of forming at least a bidentate coordination bond together with the metal ion and the nitrogen atom of the general formula (6), and preferably has the same meaning as R ⁴ .

In the general formulas (7) and (8), R ¹⁹ , R ²⁰ , R ²² , R ²³ , and R ²⁴ each independently represent a hydrogen atom or a substituent, and the substituent is the above-described R ^{1 to} R ³ . Examples thereof include the same groups as the substituents represented. R ¹⁹ and R ²¹ are a hydrogen atom, alkyl group, aryl group, heterocyclic group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, carboxyl group, cyano group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group or nitro. Group is preferred, more preferably an alkoxycarbonyl group or a cyano group. * Has the same meaning as * in General Formulas (3) and (4).

R ²¹ represents an atomic group capable of forming at least a bidentate coordination bond together with the metal ion and the nitrogen atom of the general formula (7), and preferably has the same meaning as R ⁴ .

At least one of R ²³ and R ²⁴ represents an atomic group capable of forming at least a bidentate coordination bond together with a metal ion and the nitrogen atom of the general formula (8), and preferably has the same meaning as R ⁴ .

Y ¹ represents an aromatic hydrocarbon ring, a 5-membered or 6-membered heterocyclic ring, and may have a condensed ring. Examples of the aromatic hydrocarbon ring represented by Y ¹ include a benzene ring and a naphthalene ring, and examples of the 5-membered or 6-membered heterocyclic ring include a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, an oxazole ring, and a thiazole ring. , A triazole ring, a thiadiazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a quinoline ring, a pyrazine ring, a triazine ring, an indole ring, a benzthiazole ring and a benzimidazole ring, and the aromatic hydrocarbon ring or 5-membered Or you may have a 6-membered heterocyclic ring as a condensed ring.

Preferred examples of Y ¹ in the general formula (1) include benzene ring, furan ring, pyrrole ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, thiadiazole ring, oxazole ring, thiazole ring, pyran ring, pyridine ring. , Pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, naphthalene ring, benzofuran ring, indole ring, benzothiophene ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, purine ring, quinoline ring, isoquinoline ring, coumarin ring and A chromone ring etc. can be mentioned, Furthermore, the tautomer structure of the structure represented by General formula (3)-(8) can also be mentioned.

Y ¹ may have a substituent, and examples of the substituent include the same groups as the substituents represented by R ^{1 to} R ³ described above, preferably a halogen atom, an amino group, an alkoxy group, Amido group, carbamoyl group, nitro group and the like. When the substituents are adjacent to each other, they may be condensed with each other to form a ring.

  Hereinafter, typical specific examples of the chelatable dye represented by the general formula (1) according to the present invention will be given, but the present invention is not limited thereto.

  The chelatable dye represented by the general formula (1) can be obtained by referring to conventionally known methods described in JP-A-10-20559, JP-A-10-86517, JP-A 2001-342364, and the like. And can be easily synthesized.

[Copper compound having a specific structure]
<< Compound Represented by Formula (2) >>
In the general formula (2), Z ¹ and Z ² each independently represent a monodentate or bidentate ligand, and Z ¹ and Z ² may be linked. m and n represent 0 or 1. W ¹ represents a counter ion when a counter ion is required to neutralize the charge.

Examples of Z ¹ and Z ² include JP 2000-251957, JP 2000-311723, JP 2000-323191, JP 2001-6760, JP 2001-59062, and JP 2001-60467. Etc. are mentioned. Specifically, halogen ion, hydroxide ion, ammonia, pyridine, amine (eg, methylamine, diethylamine, tributylamine, etc.), cyanide ion, cyanate ion, thiolate ion, thiocyanate ion, and bipyridines, aminopolycarboxylic acid Various chelate ligands such as acids, 8-hydroxyquinoline and the like can be mentioned, and the chelate ligands are exemplified in “Chelical Chemistry” by Keihei Ueno.

  As a monodentate ligand, a ligand coordinated by an acyl group, carbonyl group, thiocyanate group, isocyanate group, cyanate group, isocyanate group, halogen atom, cyano group, alkylthio group, arylthio group, alkoxy group or aryloxy group Or a ligand composed of dialkyl ketone or carbonamide is preferred.

  As bidentate ligands, acyloxy group, oxalylene group, acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group, thiocarbonate group, dithiocarbonate group, trithiocarbonate A ligand coordinated by a group, an alkylthio group or an arylthio group, or a ligand comprising a dialkyl ketone or a carbonamide is preferred.

Specific examples of Z ¹ and Z ² are shown below, but the present invention is not limited to these. It should be noted that the structural formula shown here is only one of the limit structures among the possible resonance structures, and the distinction between a covalent bond (indicated by-) and a coordination bond (indicated by ...) is also formal. It does not represent an absolute distinction.

Moreover, the compound represented by the said General formula (11) is also preferable as a ligand. In the general formula (11), E ¹ and E ² represent an electron withdrawing group having a Hammett substituent constant (σp) of 0.10 or more and 0.90 or less, and R is an alkyl group, an aryl group, a heterocyclic group, an alkoxy group Represents a group, an aryloxy group, or an amino group, and may have a substituent.

Examples of the substituent having a σp value of 0.10 or more and 0.90 or less represented by E ¹ and E ² include the substituents having a σp value of 0.10 or more and 0.90 or less mentioned in the above R ^{1 to} R ^3. E ¹ and E ² are preferably halogenated alkyl groups (particularly fluorine-substituted alkyl groups), carbonyl groups, cyano groups, alkoxycarbonyl groups, alkylsulfonyl groups, alkylsulfonyloxy groups, and the like.

  Preferred substituents for R include an alkyl group, an alkoxy group, an aryloxy group, and an amino group, and more preferred are an alkyl group, an alkoxy group, and an aryloxy group.

  Specific examples of the ligand represented by the general formula (11) are shown below, but the present invention is not limited thereto.

In the general formula (2), W ¹ represents a counter ion when a counter ion is necessary to neutralize the charge. For example, a certain dye is a cation, an anion, or has a net ionic charge. Whether it depends on the metal, the ligand, and the substituent. When the substituent has a dissociable group, it may be dissociated to have a negative charge, and in this case as well, the charge of the entire molecule is neutralized by W ¹ . Typical cations are inorganic or organic ammonium ions (eg tetraalkylammonium ions, pyridinium ions), alkali metal ions and protons, while anions are specifically either inorganic or organic anions. For example, halogen anion (for example, fluoride ion, chloride ion, bromide ion, iodide ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion) ), Aryl disulfonate ions (for example, 1,3-benzenedisulfonate ions, 1,5-naphthalenedisulfonate ions, 2,6-naphthalenedisulfonate ions), alkyl sulfate ions (for example, methyl sulfate ions), sulfate ions , Thiocyanate ion, persalt Acid ion, tetrafluoroborate ion, hexafluorophosphate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion, and the like.

  Examples of such a copper compound include copper acetate, copper stearate, copper 2-ethylhexanoate, copper sulfate, and cupric chloride.

  Although the specific compound represented by General formula (2) below is given, this invention is not limited to these.

  The ligand of the copper compound represented by the general formula (11) can be synthesized with reference to JP-A Nos. 2002-332259 and 2003-237246.

(Addition amount of copper compound)
In the solid dispersion and colored fine particles according to the present invention, the content of the copper compound is preferably in the range of 0.5 to 3 moles, more preferably in the range of 1 to 2 moles, relative to the dye. By containing 1 to 3 moles of the copper compound, a sufficient concentration can be obtained, light fastness is improved, and storage stability as a fine particle dispersion is also excellent. Can be prevented.

(Production method of particles)
The electrophotographic toner of the present invention is obtained by dispersing a pigment represented by the general formula (1) of the present invention and a copper compound represented by the general formula (2) in a thermoplastic resin in a solid state. In this method, the dye and the copper compound of the present invention are particles having a particle size of 10 nm to 100 nm, and light scattering can be suppressed by having a small particle size and monodispersion. Moreover, the concealable particles that block light can be eliminated. These effects are considered to improve the transparency of the single color of the toner and further improve the transparency of the superimposed color.

  In the present invention, since the dye is not in a molecular state but in a solid state in which several particles are aggregated, migration is suppressed, and dye sublimation during heat fixing, which is generally regarded as a problem in a toner using a dye, is performed. There is no worry about oil contamination.

  Furthermore, as a method of dispersing the pigment represented by the general formula (1) and the copper compound represented by the general formula (2) in the thermoplastic resin, a resin and a dye having a composition different from that of the thermoplastic resin are used. A method of dispersing colored fine particles containing a thermoplastic resin is preferred. In this method, since the dye in the colored fine particles dissolves in the resin at the molecular level, it is 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. Furthermore, it is considered that the transparency in the superimposed color is also improved.

  An electrophotographic toner having a core-shell structure according to the present invention will be described with reference to the drawings. FIG. 1 schematically shows a cross section of toner particles of the present invention in which colored fine particles 3 are dispersed in a thermoplastic resin 2. In the toner of the present invention, as shown in FIG. 2, the colored fine particles 3 may be coated with an outer shell resin (shell) 7. In this case, the resin 4 constituting the inner (core) 6 of the colored fine particles. And thermoplastic resin (binder resin) combination is not limited, the degree of freedom of material is large, and only the outer shell resin (shell) 7 is the same for the four color toners (yellow, magenta, cyan, black) If it exists, since it can manufacture on the same manufacturing conditions, the advantage in terms of cost is also great. In addition, since there is no migration of the dye as the colorant to the outside of the colored fine particles (exposure to the surface of the colored fine particles), there is no concern of dye sublimation or oil contamination during heat fixing as in the first dispersion method.

(Method for producing solid dispersion)
A method for producing a solid dispersion, which is the first dispersion method for the dye and copper compound according to the present invention, will be described.

  The dye solid dispersion of the present invention is obtained, for example, by a submerged drying method in which a dye is dissolved (or dispersed) in a water-immiscible organic solvent such as ethyl acetate or toluene, emulsified and dispersed in water, and then the organic solvent is removed. be able to. Although the emulsifying disperser is not limited, for example, an ultrasonic disperser, a high-speed stirring disperser or the like is used.

  On the other hand, a dye solid can be mixed with a surfactant and atomized using a medium type stirrer.

  A solid dispersion obtained by a submerged drying method has a shape close to a sphere, and is more preferable because it has improved adhesion to a binder and can suppress interfacial scattering.

(Preparation method of colored fine particles)
Next, a method for producing colored fine particles according to the second dispersion method of the present invention will be described.

  The colored fine particles according to the present invention can be obtained, for example, by dissolving (or dispersing) a resin, a pigment and a copper compound in an organic solvent, emulsifying and dispersing in water, and then removing the organic solvent. When coating with a resin (shell), a monomer having a polymerizable unsaturated double bond is added to the colored fine particles, emulsion polymerization is performed in the presence of an active agent, and the core shell is deposited simultaneously with the polymerization. Colored fine particles having a structure can be obtained. 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 and a copper compound are dissolved is mixed with the aqueous dispersion of resin fine particles, and then the dye is impregnated into the resin fine particles. Thereafter, it can be obtained by various methods such as a method of forming a shell using the colored fine particles as a core.

  The shell is preferably made of an organic resin, and as a method of 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 precipitation. In the present invention, after forming colored fine particles as a core containing a dye and a copper compound and a resin, a monomer having a polymerizable unsaturated double bond is added, emulsion polymerization is performed in the presence of an activator, and simultaneously with the polymerization A method of forming a shell by depositing on the core surface is preferred.

(Core shell structure)
In the present invention, the core-shell structure means a form in which two or more kinds of resins or dyes having different compositions are present in phase separation in the particles. Therefore, the shell portion may not only cover the core portion completely, but may cover a portion of the core portion. Further, a part of the resin forming the shell may form a domain or the like in the core particle. Further, it may have a multilayer structure of three or more layers including another layer having a different composition between the core portion and the shell portion.

  In the present invention, the colored fine particles form a core-shell structure, and the colored portion formed by the resin and the dye in the colored fine particles is used as a core, which is further coated with an outer shell resin to form a core-shell structure. It is preferable.

(Core resin)
Next, the resin that forms the inside (core) of the colored fine particles according to the present invention will be described.

  The resin used for the inside (core) of the colored fine particles according to the present invention is not particularly limited as long as it has a composition different from that of the thermoplastic resin. For example, (meth) acrylate resin, polyester resin, polyamide Resin, polyimide resin, polystyrene resin, polyepoxy resin, polyester resin, amino resin, fluorine resin, phenol resin, polyurethane resin, polyethylene resin, polyvinyl chloride resin, polyvinyl alcohol resin , Polyether resins, polyether ketone resins, polyphenylene sulfide resins, polycarbonate resins, aramid resins, etc., (meth) acrylate resins, polystyrene resins, polyethylene resins, polyvinyl chloride resins are preferred. Resin, polyvinyl alcohol resin, etc. Preferably resin obtained by polymerizing a polymerizable ethylenically unsaturated double bond. Most preferred are (meth) acrylate resins and polystyrene resins.

  Here, the (meth) acrylate resin is synthesized by homopolymerizing or copolymerizing various methacrylate monomers or acrylate monomers, and by changing the monomer species and the monomer composition ratio, A (meth) acrylate resin can be obtained. Further, in the present invention, it can be used together with a (meth) acrylate monomer and also with a copolymerizable monomer having an unsaturated double bond other than the (meth) acrylate monomer, In the present invention, a plurality of other resins may be mixed together with the poly (meth) acrylate resin.

Examples of the monomer component forming the (meth) acrylate resin used in the present invention include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. , Isopropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, dimethylaminoethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, di (ethylene glycol) ethyl ether (meth) acrylate, ethylene glycol methyl ether (meth) acrylate, isobornyl (meth) acrylate, Ethyl trimethylammonium (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, 2-acetamidomethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-dimethylaminoethyl (meth) ) Acrylate, 3-trimethoxysilanepropyl (meth) acrylate, benzyl (meth) acrylate, tridecyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (Meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) ) Acrylate, glycidyl (meth) acrylate, etc., preferably (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, stearyl (meth) ) Acrylate, 2-hydroxyethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, benzyl (meth) acrylate, tridecyl (meth) acrylate, dodecyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

  Polystyrene resins include homopolymers of styrene monomers or random copolymers, block copolymers, and graft copolymers obtained by copolymerization with monomers having other unsaturated double bonds copolymerizable with styrene monomers. Can be mentioned. Furthermore, blends and polymer alloys obtained by blending such polymers with other polymers are also included. Examples of the styrene monomer include nuclear alkyl substitution such as styrene, α-methylstyrene, α-ethylstyrene, α-methylstyrene-p-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and the like. Examples thereof include nuclear halogenated styrenes such as styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromostyrene, dichlorostyrene, dibromostyrene, trichlorostyrene, and tribromostyrene. Styrene and α-methylstyrene are preferred.

  Resins used in the present invention are synthesized by homopolymerizing or copolymerizing them, for example, copolymer resins such as benzyl methacrylate / ethyl acrylate or butyl acrylate, methyl methacrylate / 2-ethylhexyl methacrylate, etc. A copolymer resin of methyl methacrylate / methacrylic acid / stearyl methacrylate / acetoacetoxyethyl methacrylate, a copolymer resin of styrene / acetoacetoxyethyl methacrylate / stearyl methacrylate, and styrene / 2- Examples include copolymers of hydroxyethyl methacrylate / stearyl methacrylate, and copolymer resins such as 2-ethylhexyl methacrylate / 2-hydroxyethyl methacrylate. That.

  The resin used in the present invention preferably has a number average molecular weight of 500 to 100,000, particularly 1,000 to 30,000 from the viewpoint of durability and fine particle formability.

(Outer shell resin)
In the present invention, the outer shell resin that covers the outer shell of the colored fine particles to form the shell is not particularly limited. For example, poly (meth) acrylate resin, polyester resin, polyamide resin, polyimide resin, Polystyrene resins, polyepoxy resins, polyester resins, amino resins, fluorine resins, phenol resins, polyurethane resins, polyethylene resins, polyvinyl chloride resins, polyvinyl alcohol resins, polyarylate resins, poly Examples thereof include ether resins, polyether ketone resins, polyphenylene sulfide resins, polycarbonate resins, and aramid resins. In particular, from the viewpoint of combination with a toner binder resin (thermoplastic resin), poly (meta ) Acrylate resin.

  Here, the poly (meth) acrylate resin is synthesized by homopolymerizing or copolymerizing various (meth) acrylate monomers, and by changing the monomer species and the monomer composition ratio, the desired poly ( A (meth) acrylate resin can be obtained. In the present invention, a plurality of other resins can be mixed together with the poly (meth) acrylate resin.

  Examples of the monomer component forming the poly (meth) acrylate resin used in the present invention include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth). Acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, dimethylaminoethyl (meta ) Acrylate, 2-hydroxypropyl (meth) acrylate, di (ethylene glycol) ethyl ether (meth) acrylate, ethylene glycol methyl ether (meth) acrylate, isobornyl (meth) acrylate , Ethyltrimethylammonium chloride (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, 2-acetamidomethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-dimethylaminoethyl ( (Meth) acrylate, 3-trimethoxysilanepropyl (meth) acrylate, benzyl (meth) acrylate, tridecyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dodecyl (meth) acrylate, Octadecyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (Meth) acrylate, glycidyl (meth) acrylate, etc. are mentioned, but (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, stearyl ( They are meth) acrylate, 2-hydroxyethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, benzyl (meth) acrylate, tridecyl (meth) acrylate, dodecyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Preferred are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate.

  Further, the outer shell resin in the present invention may be a copolymer with a reactive emulsifier.

(Reactive emulsifier)
The reactive emulsifier preferably used in the present invention may be any of anionic and nonionic reactive emulsifiers, but compounds having the following A, B, or C substituents are preferred.

  A: A linear alkyl group, a branched alkyl group, or a substituted or unsubstituted aromatic group, and a substituent having a total carbon number of 6 or more.

  B: Nonionic substituent or anionic substituent that speaks for surface activity.

C: Polymerizable group capable of radical polymerization Examples of the linear alkyl group described in item A include a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and the like, and examples of the branched alkyl group include: 2-ethylhexyl group etc. are mentioned, As an aromatic group, a phenyl group, nonylphenyl group, a naphthyl group etc. are mentioned, for example.

  Examples of the nonionic substituent or anionic substituent that expresses the emulsifying ability (surfactant ability) described in Item B include polyethylene oxide, polypropylene oxide, polyalkylene oxide of a copolymer thereof, and the like. Specific examples of the anionic substituent include carboxylic acid, phosphoric acid, sulfonic acid, and salts thereof. Moreover, it is one of the specific examples of an anionic group that the above-mentioned anionic group was substituted at the terminal of alkylene oxide. The substituent represented by the item B is preferably an anionic group, and more preferably a terminal terminal is a salt.

  The polymerizable group capable of radical polymerization described in Section C is a group that undergoes polymerization or crosslinking reaction depending on the radical active species. For example, a vinyl group having an ethylenically unsaturated bond, an allyl group, a 1-propenyl group, Examples thereof include an isopropenyl group, an acrylic group, a methacryl group, a maleimide group, an acrylamide group, and a styryl group.

  As the reactive emulsifier used in the present invention, compounds represented by the following general formulas (A) to (C) are preferable.

In the general formula (A), R ₁ represents a straight-chain alkyl group having 6 to 20 carbon atoms, a branched alkyl group, or a substituted or unsubstituted aromatic group. For example, heptyl group or octyl group described in the above section A Group, nonyl group, decyl group, linear alkyl group such as dodecyl group, branched alkyl group such as 2-ethylhexyl group, aromatic group such as phenyl group, nonylphenyl group, naphthyl group, and the like.

R ₂ represents a substituent having a polymerizable group capable of radical polymerization, and examples thereof include an acryl group, a methacryl group, and a maleimide group that are ethylenically unsaturated bonds described in the above section C. Y ₁ represents a sulfonic acid, a carboxylic acid, or a salt thereof.

  The compound represented by the general formula (A) can be synthesized by a person skilled in the art by a known method. Further, it can be easily obtained from commercial products, for example, “Ramtel S-120”, “Ramtel S-120A”, “Ramtel S-180”, “Ramtel S-180A” manufactured by Kao Corporation, Sanyo Chemical An example is “Eleminol JS-2” manufactured by Kogyo Co., Ltd.

In the general formula (B), R ₃ has the same meaning as R _{1 in the} general formula (A), and R4 in the general formula (B) has the same meaning as R _{2 in the} general formula (A). It is. Y ₂ represents a hydrogen atom, a sulfonic acid, a carboxylic acid, or a salt thereof. AO represents an alkylene oxide.

  The compound represented by the general formula (B) can be synthesized by a person skilled in the art by a known method. Moreover, it can obtain easily from a commercial item, for example, NE such as "Adekaria soap NE-10", "Adekaria soap NE-20", "Adekaria soap NE-30" made by Asahi Denka Kogyo Co., Ltd. Series, “Adekaria Soap SE-10N”, “Adekaria Soap SE-20N”, “Adekaria Soap SE-20N”, etc., “Aqualon RN-10”, “Aquaron RN” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. -20 series such as “AQUALON RN-30”, “AQUALON RN-50”, “AQUALON HS-05”, “AQUALON HS-10”, “AQUALON HS-20”, “AQUALON HS-30”, etc. HS series or Aqualon BC series.

In the general formula (C), R ₅ has the same meaning as R _{1 in the} general formula (A), R _{6 in the} general formula (C) has the same meaning as R _{2 in the} general formula (A), and Y _{3 in the} general formula (C) has the same meaning as Y _{1 in the} general formula (A), and AO in the general formula (C) has the same meaning as AO in the general formula (B).

  The compound represented by the general formula (C) can be synthesized by a person skilled in the art by a known method. Moreover, it can obtain easily from a commercial item, for example, "AQUALON KH-05", "AQUALON KH-10", "AQUALON KH-20", etc. by Dai-ichi Kogyo Seiyaku Co., Ltd. can be mentioned.

  In the general formulas (B) and (C), the average polymerization degree n of the alkylene oxide chain (AO) is preferably 1 to 10, for example, “AQUALON KH-05” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. , “AQUALON KH-10”, “AQUALON HS-05”, “AQUALON HS-10”, and the like.

  In the present invention, the reactive emulsifier is preferably anionic. For example, the above-mentioned “ADEKA rear soap SE series” (manufactured by Asahi Denka Kogyo Co., Ltd.), “AQUALON HS series” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) ), “Latemul S Series” (Kao Corporation), “Eleminol JS Series” (manufactured by Sanyo Chemical Industries), and the like.

  In the present invention, the reaction emulsifier is used in an amount of about 100 parts by mass, generally 0.1 to 80 parts by mass, preferably 1 to 70 parts by mass of the resin forming the colored fine particles used in the present invention. Part by mass, particularly preferably 10 to 60 parts by mass is used.

(Surfactant)
When emulsifying the solid dispersion and colored fine particles used in the present invention, a normal anionic emulsifier (surfactant) and / or a nonionic emulsifier (surfactant) can be used as necessary. .

  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 normal 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, and polyethoxyethylene lauryl ether. Polyoxyethylene alkyl ether sulfates such as sodium sulfate, polyoxyethylene alkylaryl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate, sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, polyoxyethylene lauryl sulfosuccinic acid Examples thereof include alkylsulfosuccinic acid ester salts such as sodium and derivatives thereof.

(dye)
The dye in the solid dispersion and colored fine particles used in the present invention will be described.

The metal chelate dye used in the present invention may be used alone or in combination with other dyes. As the dye used together, generally known dyes can be used. It is preferable that the material is 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 them 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, VariFast Blue 2606, VariFast Blue 1603, Oil Yellow GG-S, Oil Yellow 3G, Oil Yellow 129, Oil Yellow 107, Oil Yellow 105, Oil Rail 105, Oil Rail 105 ed 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 5970, Oil Black 5906, Oil Black 5905, KayaseKetYKetYCL YK made by Nippon Kayaku Co., Ltd. , Kayset Yellow AG, Kayase Yellow 2G, Kayase Red SF-4G, Kayase Red K-BL, Kayase Red A-BR, Kayase Magenta 312, Kayset Blue K-FL, Arimoto Chemical Y F , FS Cyan 1522, FS Blue 1504, . 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, Mitsui Chemicals MS Yellow HD-180, MS Red G, MS Msgenta HM-1450H, MS Blue HM-1384, Sumitomo Chemical ES Red 3001, ES Red 3002 , 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 Violet 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.

  In addition, as oil-soluble dyes, cyclic methylene compounds such as phenol, naphthols, pyrazolone and pyrazolotriazole, couplers such as open-chain methylene compounds, p-diaminopyridines, azomethine dyes, indoaniline dyes and the like are also preferably used.

(Particle size)
The solid dispersion and colored fine particles in the present invention preferably have a volume-based median diameter in the range of 10 nm to 100 nm, more preferably 10 nm to 50 nm. When the volume-based median diameter is 10 nm or less, the surface area per unit volume becomes very large, so that the stability of the dye solid dispersion tends to deteriorate and the storage stability tends to deteriorate. When the particle size exceeds 100 nm, the saturation per unit color material amount in the toner is lowered. The volume-based median diameter can be determined by 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, the microtrack UPA-150 is used. It is preferable to obtain the dynamic light scattering method using (Nikkiso Co., Ltd.).

(Thermoplastic resin)
As the thermoplastic resin (binder resin) contained in the toner of the present invention, a thermoplastic resin having high adhesion to a solid dispersion and colored fine particles is preferable, and a solvent-soluble one is particularly preferable. 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, silicon resins, olefin resins, amide resins, or epoxy resins are preferably used. However, in order to improve transparency and color reproducibility of superimposed images, transparency is high and melting characteristics are high. Resins with low viscosity and high sharp melt properties are required. As the binder resin having such characteristics, styrene resin, acrylic resin, and polyester resin are suitable.

  As the binder resin, the number average molecular weight (Mn) is 3000 to 6000, preferably 3500 to 5500, and the ratio Mw / Mn of the mass average molecular weight (Mw) to the number average molecular weight (Mn) is 2 to 6, preferably It is desirable to use a resin having a glass transition point of 2.5 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. Further, if Mw / Mn is less than 2, high temperature offset is likely to occur, and if it is greater than 6, sharp melt characteristics at the time of fixing are lowered, and toner translucency and color mixing at the time of full color image formation are lowered. 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.

(toner)
In the toner of the present invention, a known charge control agent, offset preventive agent, and the like can be used in addition to the above-described thermoplastic resin and solid dispersion or colored fine particles.

  The charge control agent is not particularly limited. As the negative charge control agent used for 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, A calixarene compound, an organic boron compound, a fluorine-containing quaternary ammonium salt compound or the like is preferably used. Examples of the salicylic acid metal complex include those described in JP-A Nos. 53-127726 and 62-145255, and examples of calixarene compounds include those described in JP-A No. 2-201378. However, as the organic boron compound, for example, 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. 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.

  The toner of the present invention uses the above-described thermoplastic resin (binder resin), colored fine particles and other desired additives, kneading / pulverizing method, suspension polymerization method, emulsion polymerization method, emulsion dispersion granulation method, capsule It can manufacture by other well-known methods, such as chemical conversion method. 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, a thermoplastic resin emulsion produced by emulsion polymerization is mixed with a dispersion of toner particle components such as other colored fine particles, and the repulsive force of the particle surface generated by pH adjustment and the cohesive force due to the addition of an electrolyte are added. Toner particles are produced by slowly agglomerating while maintaining a balance, performing aggregation while controlling the particle size and particle size distribution, and simultaneously controlling the fusion and shape between the fine particles by heating and stirring. The toner particles according to 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 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 acid can be used, and it is possible to use single or different additives in combination. These fine particles are preferably used after being surface-treated with a silane coupling agent, a titanium coupling agent, a higher fatty acid, silicon oil, etc. from the viewpoint of environmental stability and heat-resistant storage stability, and the amount added is 100 parts by mass of the toner. 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 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 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, such a magnetic material. A resin-coated carrier obtained by coating 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, it is possible to use a resin-coated carrier using a silicone resin, a copolymer resin (graft resin) of an organopolysiloxane and a vinyl monomer, or a polyester resin 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 size 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 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 according to 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 photosensitive member on which the first and second images are formed is uniformly charged, and exposure according to the third image is given, and the third development is performed to form a third toner image on the photosensitive member. . Further, the photosensitive member on which the first, second, and third images are formed is uniformly charged to give exposure according to the fourth image, and the fourth development is performed, and the fourth toner image is formed on the photosensitive member. To form.

  For example, a full-color toner image is formed on the photoreceptor 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 causes image disturbance is one. The image quality can be improved by using only once.

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

  Further, 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 batch transferring the image.

  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, silicon 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 toner of the present invention, the state of transfer to fixing is such that the toner of the present invention transferred onto a transfer material is discolored even after fixing. Without being adhered to the surface of the paper in a state of being dispersed 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 a toner in which a dye obtained by dispersing or dissolving a dye as it is in a thermoplastic resin (toner binder resin) as in the prior art is exposed on the surface of the toner particles.
1. Low charge,
2. Large difference in charge between high temperature and high humidity and low temperature and low humidity (environment-dependent)
3. The amount of charge varies for each color toner when using pigments such as cyan, magenta, yellow, and black as in the case of full color image recording, for example,
Etc. can be wiped off.

  In addition, when heat-fixing to a transfer material, the dye as a colorant does not migrate out of the colored fine particles (exposed to the surface of the colored fine particles). There is no dye sublimation or oil contamination during fixing.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these.

[Preparation Example 1: Preparation of dye solid dispersion 1]
80.0 g of an aqueous solution containing 3.0 g of the dye (A-1) and surfactant EM-27C 27% solution (manufactured by Kao Corporation) was placed in a stainless beaker, and Ultra Turrax UTC (manufactured by IKA) ) And mixed and stirred. Subsequently, using a medium type stirrer SLC-12 (manufactured by Getzman, Germany), dispersion was carried out for 3 hours using 0.5 mmφ zirconia beads to obtain a dye solid dispersion 1.

[Preparation Example 2: Preparation of dye solid dispersion 6]
3.0 g of the dye (A-1) and 50.0 g of ethyl acetate were placed in a separable flask, the inside of the flask was replaced with nitrogen gas, and the mixture was stirred to completely dissolve the dye. Next, 80.0 g of an aqueous solution containing 3.0 g of a surfactant EM-27C 27% solution (manufactured by Kao Corporation) was dropped and stirred, and then an ultrasonic disperser UH-600 (manufactured by SMT Co.). Was emulsified for 5 minutes. Thereafter, ethyl acetate was removed under reduced pressure to obtain a dye solid dispersion 2.

[Preparation Example 3: Preparation of Dye Solid Dispersion 3]
(Preparation Example 1: Dye Solid Dispersion 1) Preparation of Dye (A-1) was changed to D-4: 1.10 g, and copper compound (C-28): 1.90 g was added in the same manner. Thus, “Dye solid dispersion 3” was obtained.

[Preparation Example 4: Preparation of dye solid dispersion 4]
(Preparation Example 3: Dye Solid Dispersion 3) Preparation of Dye (A-1) was changed to D-4: 1.10 g, and copper compound (C-28): 1.90 g was added in the same manner. In this way, “Dye solid dispersion 4” was obtained.

[Preparation Examples 5 to 26: Preparation of dye solid dispersions 5 to 26]
In the preparation of (Preparation Example 4: Dye Solid Dispersion 4), “Dye Solid Dispersions 5 to 26” were obtained in the same manner except that Dye D-38 and Copper Compound C-28 were changed as shown in Table 2.

  Table 2 shows the molar ratio of the types and amounts of the pigment and copper compound in the dye solid dispersions 1 to 26.

[Preparation Example 27: Preparation of colored fine particle dispersion 27]
13.5 g of the resin (P-1) having the following constitution, 16.0 g of the above-mentioned dye (A-1) which is a nickel chelate pigment, and 123.5 g of ethyl acetate are placed in a separable flask, and the inside of the flask is filled with nitrogen gas. And the mixture was stirred to completely dissolve the dye.

  Next, 238 g of an aqueous solution containing 8.0 g of Aqualon KH-05 (Daiichi Kogyo Seiyaku Co., Ltd.) was dropped and stirred, and then “Clear Mix W Motion CLM-0.8W” (M Technique) was used. Emulsified for 2 seconds.

  Thereafter, ethyl acetate was removed under reduced pressure to obtain a core-type “colored fine particle dispersion 27” impregnated with the dye.

Resin (P-1): St / HEMA / SMA = 30/40/30
St: Styrene HEMA: 2-Hydroxyethyl methacrylate SMA: Stearyl methacrylate [Preparation Example 28: Preparation of colored fine particle dispersion 28]
0.5 g of potassium persulfate was further added to the core-type colored fine particle dispersion impregnated with the dye prepared in Preparation Example 27, heated to 70 ° C. with a heater, and then 10.0 g of methyl methacrylate. The core shell type “colored fine particle dispersion liquid 28” was obtained by reacting for 5 hours while dropping.

[Preparation Example 29: Preparation of colored fine particle dispersion 29]
(Preparation Example 27: Colored fine particle dispersion 27) In the same manner except that the dye (A-1) was changed to D-38: 8.09 g and the copper compound (C-18): 7.91 g was added. Thus, a core type “colored fine particle dispersion 29” was obtained.

[Preparation Example 30: Preparation of colored fine particle dispersion 30]
(Preparation Example 28: Colored fine particle dispersion 28) In the same manner except that the dye (A-1) was changed to D-38: 8.09 g and the copper compound (C-18): 7.91 g was added. As a result, a core-shell type “colored fine particle dispersion 30” was obtained.

[Preparation Examples 31 to 47: Preparation of colored fine particle dispersions 31 to 47]
In the same manner as in Preparation Example 30: Preparation of colored fine particle dispersion 30 except that the dye (D-38) and the copper compound (C-18) were changed as shown in Table 3, the core-shell type “colored fine particle dispersion” Liquids 31 to 47 "were obtained.

  Table 3 shows the molar ratio of the pigments and copper compounds in the colored fine particle dispersions 27 to 47 and the amount added.

<Preparation of toner>
[Example of thermoplastic resin (latex) preparation]
An interface in which 7.08 g of an anionic surfactant (sodium dodecylbenzenesulfonate: SDS) was previously dissolved in 2760 g of ion-exchanged water in a 5000 ml separable flask equipped with a stirrer, a temperature sensor, a condenser, and a nitrogen introducing device. The activator solution (aqueous medium) was charged, and the internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream. On the other hand, 72.0 g of a compound represented by the following formula (1) as a release agent is added to a monomer mixed solution composed of 115.1 g of styrene, 42.0 g of n-butyl acrylate, and 10.9 g of methacrylic acid, A monomer solution was prepared by heating to 80 ° C. and dissolving. The monomer solution (80 ° C.) is mixed and dispersed in the surfactant solution (80 ° C.) by a mechanical disperser having a circulation path to obtain emulsified particles (oil droplets) having a uniform dispersed particle size. A dispersion was prepared. Next, an initiator solution prepared by dissolving 0.84 g of a polymerization initiator (potassium persulfate: KPS) in 200 g of ion-exchanged water is added to this dispersion, and the system is heated and stirred at 80 ° C. for 3 hours. Polymerization (first stage polymerization) was performed to prepare a latex. Next, an initiator solution prepared by dissolving 7.73 g of a polymerization initiator (KPS) in 240 ml of ion exchange water was added to this latex, and after 15 minutes, at 80 ° C., 383.6 g of styrene and n-butyl acrylate 140 A monomer mixture composed of 0.0 g, methacrylic acid 36.4 g, and tert-dodecyl mercaptan 13.7 g was added dropwise over 126 minutes. After completion of dropping, the mixture was heated and stirred for 60 minutes to perform polymerization (second stage polymerization), and then cooled to 40 ° C. to obtain a latex. This latex is referred to as “latex (1)”.

(Toner preparation 1)
1250 g of “Latex (1)” obtained in the thermoplastic resin (latex) preparation example, 2000 g of ion-exchanged water, and a dispersion of “Dye solid dispersion 1” obtained as described above were heated to a temperature. The mixture was stirred in a 5-liter four-necked flask equipped with a sensor, a condenser, a nitrogen introducing device, and a stirring device. After adjusting the internal temperature to 30 ° C., a 5 mol / liter aqueous sodium hydroxide solution was added to this solution to adjust the pH to 10.0. Next, an aqueous solution in which 52.6 g of magnesium chloride hexahydrate was dissolved in 72 ml of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After standing for 3 minutes, temperature increase was started, and the system was heated to 90 ° C. over 6 minutes (temperature increase rate = 10 ° C./min). In this state, the particle size of the associated particles was measured with “Coulter Counter TA-II”, and when the volume average particle size reached 6.5 μm, an aqueous solution in which 115 g of sodium chloride was dissolved in 700 g of ion-exchanged water was added. Then, the particle growth was stopped, and the fusion was continued by heating and stirring at a liquid temperature of 90 ° C. ± 2 ° C. for 6 hours. Then, it cooled to 30 degreeC on the conditions of 6 degreeC / min. Then, the associated particles are filtered from the dispersion liquid of the associated particles, and after being redispersed in ion exchange water (pH = 3) in an amount 10 times the mass ratio of the entire associated particles, The process of separating the associated particles from the washing water was repeated twice, followed by washing with ion-exchanged water alone and drying with hot air at 40 ° C. to obtain toner particles. The toner particles thus obtained are referred to as “toner particles 1”.

(Toner preparation 2 to 26)
Toner particles were obtained in the same manner as in toner preparation 1, except that the dispersion of “dye solid dispersion 1” was changed to “dye solid dispersions 2 to 26”, respectively. The toner particles thus obtained are referred to as “toner particles 2 to 26”.

(Toner preparation 27-47)
Toner particles were obtained in the same manner as in toner preparation 1, except that the dispersion of “dye solid dispersion 1” was changed to “colored fine particle dispersions 27 to 47”. The toner particles thus obtained are referred to as “toner particles 27 to 47”.

(Toner Preparation 48)
Prepare a concentrate of the mixture of D-38 and copper compound C-18, which are exemplified compounds, in an acetone solution and D-XX and C-YY mixed at a molar ratio of 1: 1. Dye was used.

  100 parts of a polyester resin, 2 parts of the chelate dye, and 3 parts of polypropylene were mixed, kneaded, pulverized, and classified to obtain a powder having an average particle size of 8.5 μm. Furthermore, 100 parts of this powder and 1.0 part of silica fine particles (particle diameter 12 nm, hydrophobization degree 60) were mixed with a Henschel mixer. The toner particles thus obtained are referred to as “toner particles 48”.

(Toner Preparation 49)
While heating low molecular weight polypropylene (number average molecular weight = 3200), a low molecular weight polypropylene emulsified dispersion emulsified in water so as to have a solid content concentration of 30% by mass with a surfactant was prepared. 60 g of the low molecular weight polypropylene emulsified dispersion prepared above and 338 g of the dispersion of colored fine particles 3 were mixed, and further, 220 g of styrene monomer, 40 g of n-butyl acrylate monomer, 12 g of methacrylic acid monomer and a chain transfer agent, t- After adding 5.4 g of dodecyl mercaptan and 2000 ml of degassed pure water, emulsion polymerization was carried out by maintaining at 70 ° C. for 3 hours while stirring under a nitrogen stream.

  After adding sodium hydroxide to the obtained resin fine particle dispersion to adjust the pH to 7.0, 700 g of a 2.7 mol% aqueous potassium chloride solution is added, and 420 ml of isopropyl alcohol and polyoxyethylene are added. 23.4 g of octyl phenyl ether (ethylene oxide average polymerization degree = 10) was dissolved in 175 g of pure water and added, and the reaction was carried out with stirring at 75 ° C. for 6 hours. Then, it cooled to 30 degreeC on the conditions of 6 degreeC / min. Then, the particles are filtered from the dispersion of the toner particles, and are redispersed in ion exchange water (pH = 3) in an amount 10 times the mass ratio with respect to the entire particles. After repeating the process of separating the toner particles from the toner twice, the toner particles were washed with only ion-exchanged water and dried with hot air at 40 ° C. to obtain toner particles. The toner particles thus obtained are referred to as “toner particles 49”.

(Comparative toner preparation 50)
In toner preparation 49, the dye was changed to C.I. I. Toner particles were obtained in the same manner except that Pigment Red 48: 3 (Clariant Japan) was used. The toner particles thus obtained are referred to as “toner particles 50”.

(Comparative Toner Preparation 51)
In toner preparation 49, the dye was changed to C.I. I. Toner particles were obtained in the same manner except that Pigment Blue 15: 3 (Dainippon Ink Co., Ltd.) was used. The toner particles thus obtained are referred to as “toner particles 51”.

(Developer preparation)
To each of the toner particles 1 to 51 obtained as described above, hydrophobic silica (number average primary particle size = 12 nm, degree of hydrophobicity = 68) is added at a ratio of 1% by mass, and hydrophobic oxidation is performed. Titanium (number average primary particle size = 20 nm, degree of hydrophobicity = 63) was added at a ratio of 1.2% by mass and mixed with a Henschel mixer to obtain a toner. These toners are referred to as “toner 1” to “toner 51”, respectively, corresponding to the toner particles.

  Each of the toners obtained as described above was mixed with a silicon carrier-coated ferrite carrier having a volume average particle diameter of 60 μm to prepare a developer having a toner concentration of 6%. These developers are referred to as “Developer 1” to “Developer 51”, respectively, corresponding to the toner.

(Evaluation equipment, conditions)
For each of “Developer 1” to “Developer 38” obtained as described above, the digital copier “Konica 7075” (manufactured by Konica Minolta Business Technologies, Inc.), in which the configuration of the fixing device is changed to the following configuration, is used. ) Was used in a normal temperature and humidity environment (temperature 25 ° C., relative humidity 55%), using a high-quality paper (64 g / m ² ) and an OHP transparent sheet as a transfer medium, and a live-action test was performed.

[Charging of photoconductor]
Photoconductor surface potential: -700V
[Development conditions]
DC bias: -500V
Dsd (distance between the photoconductor and the developing sleeve): 600 μm
Developer layer regulation: Magnetic H-Cut system Developer layer thickness: 700 μm
Developing sleeve diameter: 40 mm.

[Fixer]
As the fixing device, a heat roll fixing type was used. Specifically, a cylindrical (made of an inner diameter = 40 mm, wall thickness = 1.0 mm, overall width = 310 mm) cored bar made of an aluminum alloy with a built-in heater in the center 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 silicon rubber (Asker C The pressure roller was configured 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 each other with a load of 150 N to form a 5.8 mm wide nip. Using this fixing device, the linear velocity of printing was set to 480 mm / sec. As a cleaning mechanism for the fixing device, a web-type supply system impregnated with polydiphenyl silicon (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 175 ° C.). The application amount of silicon oil was 0.1 mg / A4.

(Characteristic evaluation)
The obtained real print was evaluated for (1) color gamut, (2) transparency, (3) chargeability, (4) offset resistance, and (5) light resistance. The evaluation criteria are ◎◎, ◎, ○ are acceptable, and Δ, × are unacceptable.

(1) Color reproducibility The color reproducibility was evaluated according to the following evaluation criteria by visual evaluation using a monitor of 10 persons, using high-quality paper as a transfer medium. The toner adhesion amount was evaluated in the range of 0.7 ± 0.05 (mg / cm ² ). The results are shown in Table 4 below.

(Evaluation criteria)
A: Color reproducibility is particularly excellent. B: Color reproducibility is excellent. B: Some color contamination is present, but there is no problem in practical use. X: Color contamination is large and image quality is problematic.

(2) Transparency The transparency of the image is achieved by using a transparent sheet for OHP as a transfer medium, creating a transmission image, and carrying the toner with a “330-type self-recording spectrophotometer” (manufactured by Hitachi, Ltd.). The visible spectral transmittance of the image was measured using a transparent sheet for OHP as a reference, the difference in spectral transmittance between 650 nm and 450 nm for yellow toner, the difference in spectral transmittance between 650 nm and 550 nm for magenta toner, and the cyan toner Then, the difference in spectral transmittance between 500 nm and 600 nm was determined, and the transparency of the OHP image was evaluated as follows. When this value is 70% or more, it can be determined that the film has good permeability. The toner adhesion amount was evaluated in the range of 0.7 ± 0.05 (mg / cm ² ).

(Evaluation criteria)
A: 90% or more B: 70% to less than 90% X: less than 70% (3) Change in charge amount with time The change in charge amount with time is the charge when the developer is set and the first image is displayed. The amount was Qa, the charge amount when 1 million images were taken out was Qb, and the value of Qb / Qa was evaluated according to the following evaluation criteria.

(Evaluation criteria)
◎: 0.9 or more and less than 1.1 ○: 0.8 or more and less than 0.9, or 1.1 or more and less than 1.2 Δ: 0.7 or more and less than 0.8, or 1.2 or more and less than 1.3 X: Less than 0.7 or 1.3 or more (4) Offset resistance The offset resistance is a high-quality A4 paper that uses a high-quality paper as a transfer medium and has a solid band-like image with a width of 5 mm in the direction perpendicular to the conveying direction. Are transported and fixed 10,000 sheets by vertical feeding, then A4 images having a halftone image of 20 mm width perpendicular to the transport direction are transported continuously by 10,000 sheets and temporarily stopped. After stopping the machine overnight, the machine was started up again, and the presence or absence of image contamination due to the fixing offset phenomenon occurring on the first sheet was visually evaluated according to the following evaluation criteria.

(Evaluation criteria)
◎: No stain on image ○: Very slight stain on image (no problem in practical use)
X: There is a stain on the image and it is not suitable for practical use.

(5) Light resistance Regarding light resistance, after measuring the image density Ci immediately after recording, the image was irradiated with xenon light (85,000 lux) for 10 days using a weather meter “Atlas C.165”. Thereafter, the image density Cf was measured again, and the dye residual ratio (((Ci−Cf) / Ci) × 100%) was calculated and evaluated 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”.

(Evaluation criteria)
A: Dye remaining ratio is 95% or more A: Dye remaining ratio is 90% or more and less than 95% B: Dye remaining ratio is 80% or more and less than 90% Δ: Dye remaining ratio is 70% or more and less than 80% X: Dye remaining The rate is less than 70%.

  Table 4 shows the evaluation results.

  From the evaluation results, “Developers 3 to 23” and “Developers 26 to 43” of the present invention have excellent color reproducibility, transparency, chargeability and offset resistance, and ensure high-quality images. Can be formed. In addition, even when observing the fixing roller and the collected silicon oil, it can be seen that there is no coloring by the dye. Moreover, it turns out that the metal chelate pigment | dye which concerns on this invention which is equivalent or more compared with a nickel chelate pigment | dye (dye (A-1)), and is safe also about the light resistance is excellent.

FIG. 3 is a diagram schematically illustrating a cross section of toner particles in which colored fine particles are dispersed in a thermoplastic resin. It is the figure which represented typically the cross section of the colored fine particle of the core shell structure formed by coat | covering an inside (core) with outer shell resin (shell).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Toner particle 2 Thermoplastic resin 3 Colored fine particle 4 Resin 5 Dye 6 Inside (core)
7 Outer shell resin (shell)

Claims (11)

An electrophotographic toner comprising a thermoplastic resin in which a dye represented by the following general formula (1) and a copper compound represented by the general formula (2) are dispersed.

[Wherein R ¹ , R ² and R ³ each represent a hydrogen atom or a substituent, and X ¹ is an atom necessary for forming a 5-membered or 6-membered heterocyclic ring containing at least one nitrogen atom. Represents a group, may form a condensed ring, and may have a substituent. Y ¹ represents an aromatic hydrocarbon ring, a 5-membered or 6-membered heterocyclic ring, may form a condensed ring, and may have a substituent. R ⁴ represents an atomic group capable of forming at least a bidentate coordination bond with the metal ion and the nitrogen atom of X ¹ . ]
Formula (2) Cu ²⁺ (Z ¹ ) p (Z ² ) q · W ¹
[Wherein, Z ¹ and Z ² each independently represent a monodentate or bidentate ligand, and may be the same or different, and Z ¹ and Z ² may be linked. p and q represent the integer of 0-2. W ¹ represents a counter ion when a counter ion is required to neutralize the charge. ] In the general formula (1), at least one of R ¹ , R ² and R ³ is an electron withdrawing group having a Hammett substituent constant (σp) of 0.1 or more and 0.9 or less. The toner for electrophotography described in 1. 3. The electrophotographic toner according to claim 1, wherein X ¹ in the general formula (1) is a group represented by the following general formula (3) or (4).

[Wherein, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ each independently represents a hydrogen atom or a substituent, and at least one of R ¹⁰ , R ¹¹ is a metal ion and nitrogen of the general formula (3) R ¹³ represents an atomic group capable of forming at least a bidentate coordination bond with the atom, R ¹³ represents an atomic group capable of forming at least a bidentate coordination bond with the nitrogen atom of the general formula (4), and * It represents a binding site with the carbon atom to which X ^{1 of the} trimethine dye represented by the general formula (1) is bonded. ] 3. The electrophotographic toner according to claim 1, wherein X ¹ in the general formula (1) is a group represented by the following general formula (5) or (6).

[Wherein, R ¹⁵ and R ¹⁷ each independently represents a hydrogen atom or a substituent, and R ¹⁶ represents an atomic group capable of forming at least a bidentate coordination bond with the nitrogen atom of the general formula (5); R ¹⁸ represents an atomic group capable of forming at least a bidentate coordination bond together with the metal ion and the nitrogen atom of the general formula (6), and * represents the trimethine dye X ¹ represented by the general formula (1). Represents the bonding site with the bonded carbon atom. ] 3. The electrophotographic toner according to claim 1, wherein X ¹ in the general formula (1) is a group represented by the following general formula (7) or (8).

[Wherein, R ¹⁹ , R ²⁰ , R ²² , R ²³ , R ²⁴ each independently represents a hydrogen atom or a substituent, and R ²¹ represents at least a bidentate together with a metal ion and a nitrogen atom of the general formula (7). Represents a group of atoms capable of forming a coordination bond, and at least one of R ²³ and R ²⁴ represents an atomic group capable of forming at least a bidentate coordination bond with the nitrogen atom of the general formula (8); It represents a binding site with the carbon atom to which X ^{1 of the} trimethine dye represented by the general formula (1) is bonded. ] 6. The electrophotographic toner according to claim 1, wherein R ⁴ in the general formula (1) is represented by any one of the following general formulas (9) and (10). .

[In the formula, Z ³ represents an atomic group that forms a 5- or 6-membered nitrogen-containing aromatic heterocycle with a nitrogen atom, R ³¹ represents a hydrogen atom or a substituent, and L ¹ has 1 or 2 carbon atoms. Q ¹ represents a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, an alkylsulfonylamino group, or an arylsulfonylamino group. ] Any one of the preceding claims, wherein the ligand (Z ¹ or Z ²⁾ of the general formula (2) a copper compound represented by at least one of a following general formula (11) The toner for electrophotography described in 1.

(In the formula, E ¹ and E ² represent an electron-withdrawing group having a Hammett substituent constant (σp) of 0.1 to 0.9, and R represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryl group. Represents an oxy group or an amino group and may have a substituent.) A dispersion obtained by emulsifying and dispersing the dye represented by the general formula (1) and the copper compound represented by the general formula (2) in water and a thermoplastic resin are dispersed. The toner for electrophotography according to any one of claims 1 to 7. The colored fine particles obtained by emulsifying and dispersing in water the dye medium resin having a composition different from the dye represented by the general formula (1), the copper compound represented by the general formula (2) and the thermoplastic resin are thermoplastic. The electrophotographic toner according to claim 1, wherein the toner is dispersed with a resin. 10. The electrophotographic toner according to claim 9, wherein the colored fine particles comprise a core containing a resin and a dye and an outer shell resin (shell) covering the core. An image forming method comprising at least a step of developing an electrostatic charge image formed on an electrostatic image bearing member with toner, and a step of transferring a toner image formed by development onto a transfer material. 11. An image forming method using the electrophotographic toner according to any one of 10 above.

Images