JP2015161825A - Toner for electrostatic charge image development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which can inhibit an image fog in continuous printing and output an image having stably high saturation and high concentration.SOLUTION: A toner for electrostatic charge image development comprises at least a binder resin, a colorant comprising a dye represented by the general formula (1) and a metal compound separately defined, and an external additive comprising silica fine particles of 60-150 nm in volume average primary particle diameter formed by a sol gel method.

Description

  The present invention relates to a toner for developing an electrostatic image.

  Color image formation by electrophotography was initially popular for office use, but due to its speed and ease of handling, it has recently become popular in the light printing field called on-demand printing (POD). It has become. This is due to the fact that the printing work required for the printing method is not necessary, and the image quality required for the printed image can be realized by the electrophotographic method due to the recent progress of digital technology. It can be said. Due to the widespread use in the field of light printing, market demands are increasing to ensure a wider color reproduction area such as Japan Color certification for color reproducibility and to stabilize color reproduction even in continuous printing of multiple sheets. . As a color toner for forming such a color image, a yellow toner, a magenta toner, a cyan toner, or the like containing a binder resin (binder resin) made of a thermoplastic resin and a colorant of each color is used. ing.

  As means for realizing good color reproducibility, Patent Document 1 discloses a toner containing a colorant composed of a reaction compound produced by a reaction between a colorant precursor and a metal-containing compound. As a means for obtaining a high density image, Patent Document 2 discloses a toner containing large-diameter inorganic fine particles.

JP 2010-2897 A JP 2002-108001 A

  However, although the toner described in Patent Document 1 can achieve a high-saturation image, it has a dye-derived colorant and thus tends to cause image defects with image fogging when continuously printed. . In addition, the toner described in Patent Document 2 has been difficult to achieve a stable image density for a long time during continuous printing.

  Accordingly, an object of the present invention is to provide a toner for developing an electrostatic charge image that can suppress the occurrence of image fogging during continuous printing and can stably output an image with high saturation and high density.

  The inventors of the present invention have accumulated extensive research. As a result, surprisingly, a binder resin, a colorant composed of a dye represented by the following general formula (1) and a metal compound represented by the following chemical formula (2), and a volume average formed by a sol-gel method It has been found that the above problems can be solved by an electrostatic charge image developing toner containing an external additive containing silica fine particles having a primary particle size of 60 to 150 nm, and has completed the present invention.

  That is, the above object of the present invention is achieved by the following configuration.

  1. At least a binder resin, a colorant composed of a dye represented by the following general formula (1) and a metal compound represented by the following chemical formula (2), and a volume average primary particle size formed by a sol-gel method is 60 to 150 nm. And an external additive containing silica fine particles, and an electrostatic charge image developing toner:

In the general formula (1),
Rx ₁ and Rx ₂ are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Lx is a hydrogen atom or a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Gx ₁ is a linear, branched, or cyclic alkyl group or unsubstituted C2-20 substituted,
Gx ₂ is a substituted or unsubstituted linear or branched alkyl group having 1 to 5 carbon atoms,
Gx ₃ is a hydrogen atom, a halogen atom, a group represented by Gx ₄ —CO—NH—, or a group represented by Gx ₅ —N (Gx ₆ ) —CO—, wherein Gx ₄ is a substituent. Gx ₅ and Gx ₆ are each independently a hydrogen atom or a substituent,
Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently a hydrogen atom or a substituent,

In the general formula (2),
M is a divalent metal,
R ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
R ₂ is a hydrogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a halogen atom, or a cyano group,
R ₃ is a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms.

  2. 1. having a core-shell structure comprising a core part and a shell part; The toner for developing an electrostatic charge image according to 1.

  3. 1. The resin constituting the shell part is a polyester resin. The toner for developing an electrostatic charge image according to 1.

  4). 1. The glass transition temperature of the resin constituting the shell part is 45 to 65 ° C. Or 3. The toner for developing an electrostatic charge image according to 1.

  According to the present invention, it is possible to provide an electrostatic charge image developing toner capable of suppressing the occurrence of image fogging during continuous printing and stably outputting an image with high saturation and high density.

  The present invention includes at least a binder resin, a colorant composed of a dye represented by the following general formula (1) and a metal compound represented by the following chemical formula (2), and a volume average primary particle diameter formed by a sol-gel method. And an external additive containing silica fine particles having a particle size of 60 to 150 nm.

In the general formula (1),
Rx ₁ and Rx ₂ are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Lx is a hydrogen atom or a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Gx ₁ is a linear, branched, or cyclic alkyl group or unsubstituted C2-20 substituted,
Gx ₂ is a substituted or unsubstituted linear or branched alkyl group having 1 to 5 carbon atoms,
Gx ₃ is a hydrogen atom, a halogen atom, a group represented by Gx ₄ —CO—NH—, or a group represented by Gx ₅ —N (Gx ₆ ) —CO—, wherein Gx ₄ is a substituent. Gx ₅ and Gx ₆ are each independently a hydrogen atom or a substituent,
Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently a hydrogen atom or a substituent.

In the general formula (2),
M is a divalent metal,
R ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
R ₂ is a hydrogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a halogen atom, or a cyano group,
R ₃ is a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms.

  As means for realizing good color reproducibility, Patent Document 1 discloses a toner containing a colorant composed of a reaction compound produced by a reaction between a colorant precursor and a metal-containing compound. Further, as a means for obtaining a high density image, Patent Document 2 discloses a toner containing large-diameter inorganic fine particles.

  However, although the toner described in Patent Document 1 can achieve a high-saturation image, it contains a dye-derived colorant, so that the toner forms a soft agglomerate when exposed to stress in continuous printing. However, image defects such as image fog tend to occur easily. Further, the toner described in Patent Document 2 has a problem that it is difficult to achieve a stable image density over a long period of time because a large-diameter external additive is easily detached from the toner base particles during continuous printing. As described above, with conventional toners, even if high saturation and high density images can be realized in initial printing, it is difficult to stably output images during continuous printing, and improvement has been desired.

  On the other hand, the colorant contained in the toner of the present invention has a plastic effect on the binder resin, so that the toner surface is soft. However, a large diameter silica having a volume average primary particle size of 60 to 150 nm is externally added. By using it as an agent, the adhesion between toners is reduced and the blocking property is improved. Further, due to the softness of the toner surface, the large-diameter silica is strongly fixed to the surface of the binder resin, so that the external additive is hardly transferred. Therefore, the toner for developing an electrostatic charge image of the present invention has an image fogging effect not only at the initial stage but also at the time of continuous printing due to the synergistic effect of the colorant having a plasticizing effect of the binder resin and the external additive containing large-diameter silica. It is presumed that the image formation with high saturation and high density can be realized stably by suppressing the occurrence of the above.

  Note that the above mechanism is based on estimation, and the present invention is not limited to the above mechanism.

  Hereinafter, the configuration of the electrostatic image developing toner of the present invention will be described in detail. Hereinafter, the toner for developing an electrostatic charge image of the present invention is also simply referred to as “the toner of the present invention”.

[Binder resin]
The binder resin used in the present invention is not particularly limited, but is typically formed by polymerizing a polymerizable monomer called a vinyl monomer described below. is there. The polymer constituting the resin is obtained by polymerizing at least one type of polymerizable monomer, and the types of vinyl monomers used for the polymerization may be single or a combination of plural types.

  Specific examples of the vinyl polymerizable monomer are shown below.

(1) Styrene or styrene derivatives Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-chlorostyrene, etc. (2) Methacrylate derivatives Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, (3) Acrylic acid ester derivatives Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate , Stearyl acrylate, lauryl acrylate, phenyl acrylate, etc. (4) olefins ethylene, propylene, isobutylene, etc. (5) vinyl esters vinyl propionate, vinyl acetate, vinyl benzoate, etc. (6) vinyl ethers vinyl methyl ether, vinyl ethyl ether (7) Vinyl ketones Vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl keto (8) N-vinyl compounds N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, etc. (9) Others Vinyl compounds such as vinylnaphthalene and vinylpyridine, acrylic acid such as acrylonitrile, methacrylonitrile, acrylamide, etc. Or a methacrylic acid derivative.

  Some vinyl polymerizable monomers have an ionic dissociation group shown below. In particular, since the colorant constituting the toner used in the present invention has weak alkalinity as described above, it has an ionic dissociation group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group in the side chain of the monomer. Is preferable because it improves the dispersibility of the colorant. Specific examples of the vinyl polymerizable monomer having an ionic dissociation group include the following.

(1) Those having a carboxyl group Acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, etc. (2) Those having a sulfonic acid group Styrene sulfone Acid, allylsulfosuccinic acid, 2-acrylamido-2-methylpropanesulfonic acid and the like (3) Those having a phosphate group Acid phosphooxyethyl methacrylate and the like.

  Moreover, the resin which has a crosslinked structure is producible by using the polyfunctional vinyl shown below. Specific examples of polyfunctional vinyls are shown below. That is, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate and the like can be mentioned. .

  In addition to the above, polyvinyl chloride, epoxy resin, epoxy polyol resin, polyurethane resin, polyamide resin, polyester resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon Examples thereof include resins, aromatic petroleum resins, chlorinated paraffin, and paraffin wax.

  Moreover, the styrene acryl modified polyester resin comprised from the polyester molecule | numerator of the structure which made the molecular bond of the styrene acrylic copolymer molecular chain to the polyester molecular chain can also be illustrated.

  These binder resins can be used singly or in combination of two or more.

  The binder resin described above may have a single-layer structure or a core-shell structure, but preferably has a core-shell structure from the viewpoint that the properties of the surface of the binder resin can be more easily controlled. . That is, the toner for developing an electrostatic charge image of the present invention preferably has a core-shell structure composed of a core part and a shell part. The core-shell structure is, for example, a resin region (shell part) having a relatively high glass transition temperature on the surface of a resin particle (core particle, core part) containing a colorant or a release agent and having a relatively low glass transition temperature. ). The core-shell structure is not limited to a structure in which the shell part completely covers the core part. For example, the shell part does not completely cover the core particle (core part), and in some places the core particle (core part) Including those that are exposed.

  The cross-sectional structure of the core-shell structure can be confirmed using known means such as a transmission electron microscope (TEM) or a scanning probe microscope (SPM).

  The combination of resins constituting the core-shell structure is not particularly limited, but it is preferable to use a polyester resin having high toughness even for a low molecular weight for the shell portion.

  Further, the glass transition temperature (Tg) of the resin constituting the shell portion is 45 to 65 ° C. from the viewpoint of strongly fixing the external additive to the binder resin or suppressing the formation of toner soft aggregates. It is preferable that The glass transition temperature can be measured by a DSC method.

  Furthermore, the resin forming the core portion is formed from an aromatic vinyl monomer and a (meth) acrylate monomer from the viewpoints of dispersibility of the colorant, charging stability, cost reduction, and the like. It is preferable to use a styrene acrylic resin.

  Hereinafter, a styrene acrylic resin and a polyester resin that are suitably used as the binder resin according to the present invention will be described.

[Styrene acrylic resin]
The styrene acrylic resin referred to in the present invention is formed by polymerization using at least an aromatic vinyl monomer and a (meth) acrylic acid ester monomer. Here, the aromatic vinyl monomer includes not only styrene represented by the structural formula of CH ₂ ═CH—C ₆ H ₅ but also a structure having a known side chain or functional group in the styrene structure. It is.

The (meth) acrylic acid ester monomer has a functional group having an ester bond in the side chain. _{Specifically,} CH 2 = CHCOOR (R is an alkyl group) other acrylic acid ester monomer represented _by, methacrylic acid ester represented by _{CH 2 = C (CH 3)} COOR (R is an alkyl group) Vinyl-based ester compounds such as monomers are included.

  Specific examples of the aromatic vinyl monomer and (meth) acrylic acid ester monomer capable of forming a styrene acrylic resin are shown below, but are not limited to those shown below.

  Examples of the aromatic vinyl monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, Examples thereof include p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, and the like.

  The (meth) acrylic acid ester monomer is typically the following acrylic acid ester monomer and methacrylic acid ester monomer. Examples of the acrylic acid ester monomer include methyl acrylate, Examples include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, and phenyl acrylate phenyl. Examples of the methacrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate. Lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate and the like.

  These aromatic vinyl monomers, acrylic acid ester monomers, or methacrylic acid ester monomers can be used alone or in combination of two or more.

  In addition to the copolymer formed only with the above-mentioned aromatic vinyl monomer and (meth) acrylic acid ester monomer, the styrene acrylic resin includes these aromatic vinyl monomer and (meth) acrylic. In addition to acid ester monomers, some are formed by using general vinyl monomers in combination. Although the vinyl monomer which can be used together when forming the styrene acrylic resin said by this invention below is illustrated, the vinyl monomer which can be used together is not limited to what is shown below.

(1) Olefins Ethylene, propylene, isobutylene, etc. (2) Vinyl esters Vinyl propionate, vinyl acetate, vinyl benzoate, etc. (3) Vinyl ethers Vinyl methyl ether, vinyl ethyl ether, etc. (4) Vinyl ketones Vinyl methyl ketone, Vinyl ethyl ketone, vinyl hexyl ketone, etc. (5) N-vinyl compounds N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone, etc. (6) Others Vinyl compounds such as butadiene, vinyl naphthalene, vinyl pyridine, acrylonitrile, Acrylic acid or methacrylic acid derivatives such as methacrylonitrile, acrylamide and methacrylamide, vinyl acetate, maleic anhydride and the like.

  Moreover, it is also possible to produce a resin having a crosslinked structure by using the following polyfunctional vinyl monomer. Specific examples of the polyfunctional vinyl monomer include, for example, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl. Examples thereof include dimethacrylates and trimethacrylates of tertiary alcohols such as glycol dimethacrylate, neopentyl glycol diacrylate, hexylene glycol dimethacrylate, hexylene glycol diacrylate, pentaerythritol, and trimethylolpropane.

  0.001-5 mass% is preferable with respect to binder resin, and, as for the usage-amount of a polyfunctional vinyl monomer, 0.003-2 mass% is more preferable. By using the polyfunctional vinyl monomer, a gel component insoluble in tetrahydrofuran is generated. The gel component is preferably 40% by mass or less, more preferably 20% by mass or less of the entire binder resin. is there.

  Furthermore, it is also possible to use a vinyl monomer having an ionic dissociation group in the side chain as shown below. Specific examples of the ionic dissociation group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Specific examples of these vinyl monomers having an ionic dissociation group are shown below.

  Specific examples of the vinyl monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, and the like. .

  Specific examples of the vinyl monomer having a sulfonic acid group include styrene sulfonic acid, allyl sulfosuccinic acid, 2-acrylamido-2-methylpropane sulfonic acid, and the like. Furthermore, specific examples of the vinyl monomer having a phosphate group include acid phosphooxyethyl methacrylate and 3-chloro-2-acid phosphooxypropyl methacrylate.

  The formation method in particular of a styrene acrylic resin is not restrict | limited, The method of superposing | polymerizing a monomer using a well-known polymerization initiator is mentioned. Specific examples of the polymerization initiator will be described later.

  When forming the styrene acrylic resin used in the present invention, the content of the aromatic vinyl monomer and the (meth) acrylic acid ester monomer is not particularly limited, and the softening point temperature of the binder resin or It is possible to adjust appropriately from the viewpoint of adjusting the glass transition temperature. Specifically, the content of the aromatic vinyl monomer is preferably 40 to 95% by mass and more preferably 50 to 90% by mass with respect to the whole monomer. Moreover, 5-60 mass% is preferable with respect to the whole monomer, and, as for content of a (meth) acrylic acid ester monomer, 10-50 mass% is more preferable.

  The molecular weight of the styrene acrylic resin is preferably 2,000 to 1,000,000 in terms of weight average molecular weight (Mw). Further, the number average molecular weight (Mn) is preferably 1,000 to 100,000. Moreover, 1.5-100 are preferable and, as for molecular weight distribution (Mw / Mn), 1.8-70 are more preferable. By setting the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the styrene acrylic resin within the above ranges, an offset is applied in the fixing step when printing is performed using the prepared toner. This is effective in preventing the occurrence of phenomena. The glass transition point temperature of the styrene acrylic resin formed by radical polymerization is preferably 30 to 70 ° C, and the softening point temperature is preferably 80 to 170 ° C. When the glass transition point temperature and the softening point temperature are in the above ranges, good fixability can be obtained. The molecular weight of the styrene acrylic resin can be measured by a gel permeation chromatograph (GPC) method.

[Polyester resin]
The polyester resin used in the present invention is formed by subjecting a known polycarboxylic acid and polyhydric alcohol to a polycondensation reaction in the presence of a catalyst. As the polyester resin, it is also possible to use the aforementioned polyvalent carboxylic acid or polyhydric alcohol derivative used as a raw material. The polyvalent carboxylic acid derivative includes an alkyl ester, an acid anhydride, or an acid chloride of the polyvalent carboxylic acid. Etc. Polyhydric alcohol derivatives include polyhydric alcohol ester compounds and hydroxycarboxylic acids.

  The polyester resin may be crystalline or non-crystalline. However, when the polyester resin is used for the shell portion of the core-shell structure, the polyester resin is preferably non-crystalline from the viewpoint of blocking resistance, charging stability, and the like.

  Hereinafter, specific examples of the polyvalent carboxylic acid and polyhydric alcohol that can be used for forming the polyester resin will be described. Examples of the polyvalent carboxylic acid include known divalent carboxylic acids and trivalent or higher carboxylic acids called aliphatic dicarboxylic acids and aromatic dicarboxylic acids. Specific examples of the divalent carboxylic acid include, for example, oxalic acid, succinic acid, maleic acid, mesaconic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid. Acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-dicarboxylic acid, malic acid, citric acid, malonic acid, pimelic acid, tartaric acid, phthalic acid, isophthalic acid Terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, hexahydroterephthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycol Glycolic acid, diphenylacetic acid, diphenyl-p, '- dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, and dodecenylsuccinic acid. Specific examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid. These polyvalent carboxylic acids can be used singly or in combination of two or more.

  Specific examples of the polyhydric alcohol include known dihydric alcohols and trihydric or higher alcohols. Specific examples of the dihydric alcohol include, for example, ethylene glycol, propylene glycol, butanediol, diethylene glycol, hexanediol, cyclohexanediol, octanediol, decanediol, dodecanediol, ethylene oxide adduct of bisphenol A, and propylene oxide of bisphenol A. Examples include adducts. Specific examples of the trivalent or higher alcohol include glycerin, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, tetraethylol benzoguanamine, and the like. These polyhydric alcohols can be used alone or in combination of two or more.

  As a method for producing the polyester resin, a conventionally known production method in which a polycondensation reaction between a polyvalent carboxylic acid and a polyhydric alcohol is performed in the presence of a catalyst is employed. A known catalyst can also be used.

  The polyvalent carboxylic acid preferably contains an aliphatic unsaturated dicarboxylic acid having a carbon-carbon unsaturated bond in the molecular structure from the viewpoint of improving the resin strength. The aliphatic unsaturated dicarboxylic acid is preferably fumaric acid, maleic acid, or mesaconic acid.

  The ratio of the aliphatic unsaturated dicarboxylic acid to the total polyvalent carboxylic acid used in the production of the polyester resin is preferably 10 to 75 mol%, and more preferably 15 to 60 mol%.

  The ratio of the polyhydric carboxylic acid to the polyhydric alcohol is preferably an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] of the polyhydric alcohol to the carboxyl group [COOH] of the polyhydric carboxylic acid. 0.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2.

  The polyester resin may have a partially branched structure or a crosslinked structure by appropriately selecting the valence of the polyvalent carboxylic acid and / or polyhydric alcohol used.

[Colorant]
The colorant which concerns on this invention consists of the pigment | dye represented by General formula (1), and the metal compound represented by General formula (2).

[Dye]
The coloring matter used in the present invention is a compound represented by the following general formula (1).

In the general formula (1), Rx ₁ and Rx ₂ are each independently substituted or are or unsubstituted straight, branched, or cyclic alkyl group. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-amyl group, tert-pentyl group Group, neopentyl group, n-hexyl group, 3-methylpentan-2-yl group, 3-methylpentan-3-yl group, 4-methylpentyl group, 4-methylpentan-2-yl group, 1,3 -Dimethylbutyl group, 3,3-dimethylbutyl group, 3,3-dimethylbutan-2-yl group, n-heptyl group, 1-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5- Methylhexyl group, 1-ethylpentyl group, 1- (n-propyl) butyl group, 1,1-dimethylpentyl group, 1,4-dimethylpentyl group, 1,1-diethylpropyl group, 1 3,3-trimethylbutyl group, 1-ethyl-2,2-dimethylpropyl group, n-octyl group, 2-ethylhexyl group, 2-methylhexane-2-yl group, 2,4-dimethylpentan-3-yl Group, 1,1-dimethylpentan-1-yl group, 2,2-dimethylhexane-3-yl group, 2,3-dimethylhexane-2-yl group, 2,5-dimethylhexane-2-yl group, 2,5-dimethylhexane-3-yl group, 3,4-dimethylhexane-3-yl group, 3,5-dimethylhexane-3-yl group, 1-methylheptyl group, 2-methylheptyl group, 5- Methylheptyl group, 2-methylheptan-2-yl group, 3-methylheptan-3-yl group, 4-methylheptan-3-yl group, 4-methylheptan-4-yl group, 1-ethylhexyl group, 2 -D Ruhexyl group, 1-propylpentyl group, 2-propylpentyl group, 1,1-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 1-ethyl-1-methylpentyl group, 1 -Ethyl-4-methylpentyl group, 1,1,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 1-isopropyl-1,2-dimethylpropyl group, 1,1,3,3-tetra Methylbutyl group, n-nonyl group, 1-methyloctyl group, 6-methyloctyl group, 1-ethylheptyl group, 1- (n-butyl) pentyl group, 4-methyl-1- (n-propyl) pentyl group 1,5,5-trimethylhexyl group, 1,1,5-trimethylhexyl group, 2-methyloctane-3-yl group, n-decyl group, 1-methylnonyl group, 1-ethyloxy Octyl group, 1- (n-butyl) hexyl group, 1,1-dimethyloctyl group, 3,7-dimethyloctyl group, n-undecyl group, 1-methyldecyl group, 1-ethylnonyl group, n-dodecyl group, 1 -Methylundecyl group, n-tridecyl group, n-tetradecyl group, 1-methyltridecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n- Eicosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, or n -Triacontyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-tert-butyl-silane Rohekishiru group, and the like.

  One or more hydrogen atoms of the alkyl group may be substituted with a substituent. Examples of the substituent include alkenyl groups (for example, vinyl group, allyl group, etc.), alkynyl groups (for example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon groups (for example, phenyl group, naphthyl group, etc.), Aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, Phthalazyl group, etc.), heterocyclic group (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) Group, dodecyloxy group, etc.), cycloalkoxy group (for example, cycl Pentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group) Etc.), a cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), an arylthio group (eg, phenylthio group, naphthylthio group, etc.), an alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxy) Carbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), phosphoryl group (example) Dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylamino) Sulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2 -Ethylhexylcarbonyl group, 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, dimethyl group) Carbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (For example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, A hexylaminocarbonyl group, an octylaminocarbonyl group, a 2-ethylhexylaminocarbonyl group, a dodecylaminocarbonyl group, a phenylaminocarbonyl group, a naphthylaminocarbonyl group, a 2-pyridylaminocarbonyl group, etc.), a ureido group (for example, a methylureido group, Ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butyl) Sulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pi Dilsulfinyl 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, dibutylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group) , Naphthylamino group, 2-pyridylamino group, etc.), azo group (eg, phenylazo group), alkylsulfonyloxy group (eg, methanesulfonyloxy group), cyano group, nitro group, halogen atom (eg, fluorine atom) Child, a chlorine atom, a bromine atom, etc.), a hydroxy group, etc., and these may further have a substituent. Among these substituents, an aromatic hydrocarbon group, an alkoxy group, a cycloalkoxy group, a halogen atom, or a hydroxy group is preferable.

Rx ₁ and Rx ₂ are each independently preferably an unsubstituted alkyl group or an alkyl group substituted with an alkoxy group, and more preferably an unsubstituted alkyl group.

The total number of carbon atoms contained in the alkyl group used in Rx ₁ and carbon atoms contained in the alkyl group used in Rx ₂ is preferably 8 or more, more preferably 12 or more, and 16 More preferably, it is the above.

In the general formula (1), Lx is a hydrogen atom or a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group are the same as the alkyl groups used in the above Rx ₁ and Rx ₂ , and thus detailed description thereof is omitted here. Further, specific examples of the substituent are the same as the substituents that can be used in the above Rx ₁ and Rx ₂ , and thus detailed description thereof is omitted here. Preferably it is a C1-C5 alkyl group, More preferably, it is a methyl group or an ethyl group.

In the above general formula (1), Gx ₁ is a substituted or unsubstituted C2-C20 linear, branched, or cyclic alkyl group. Specific examples of the alkyl group are the same as the alkyl groups used in Rx ₁ and Rx ₂ except for the methyl group, and thus detailed description thereof is omitted here. Further, specific examples of the substituent are the same as the substituents that can be used in the above Rx ₁ and Rx ₂ , and thus detailed description thereof is omitted here. Preferred is a branched alkyl group, more preferred is a tertiary alkyl group, and even more preferred is a t-butyl group.

In the above general formula (1), Gx ₂ is a substituted or unsubstituted linear or branched alkyl group having 1 to 5 carbon atoms. By employing the small alkyl group with a carbon number as gx _2, reduces the hydrophobicity of the dye, the interaction with the binder resin becomes stronger. As a result, the dispersion state of the dye becomes more stable, and the toner has excellent color reproducibility even if the fixing temperature fluctuates.

Specific examples of the alkyl group used in Gx ₂ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pentyl. Group, iso-amyl group, tert-pentyl group, or neopentyl group. Specific examples of the substituent are the same as the substituents that can be used for the above Rx ₁ and Rx ₂ , and thus detailed description thereof is omitted here. From the viewpoint of obtaining the effect of the present invention more effectively, a methyl group or an ethyl group is preferred.

In the general formula (1), Gx ₃ is a hydrogen atom, a halogen atom, a group represented by Gx ₄ —CO—NH—, or a group represented by Gx ₅ —N (Gx ₆ ) —CO—. In this case, Gx ₄ is a substituent, and Gx ₅ and Gx ₆ are each independently a hydrogen atom or a substituent.

Specific examples of the substituent used in Gx ₄ , Gx _5, and Gx ₆ include linear, branched, or cyclic having 1 to 20 carbon atoms in addition to the substituent that can be used in Rx ₁ and Rx _2. Of the alkyl group.

Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently a hydrogen atom or a substituent. Specific examples of the substituent used in Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ include linear groups having 1 to 20 carbon atoms in addition to the substituents that can be used in Rx ₁ and Rx _2. , Branched or cyclic alkyl groups. Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently preferably a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, or an aryl group, and all of them are hydrogen atoms. More preferred.

  Hereinafter, although the more specific example of the pigment | dye represented by the said General formula (1) is shown, this invention is not limited to these.

  Examples of the dye represented by the general formula (1) according to the present invention include, for example, JP-A-63-226653, JP-A-10-193807, JP-A-11-78258, JP-A-6-250357, No. 2-155893, No. 1-110565, No. 2-668, No. 2-28264, No. 2-53865, No. 2-53866, British Patent No. 1,252,418 Specification, Japanese Patent Application Laid-Open No. 64-63194, Japanese Patent Application Laid-Open No. Hei 2-208094, Japanese Patent Application No. 3-205189, Japanese Patent Application No. 2-265911, Japanese Patent Application No. 2-3310087, Japanese Patent Application Laid-Open No. 4-91987, JP 63-205288, JP 3-226750, British Patent 1,183,515, JP 4-190348. JP-A-63-113077, JP-A-3-275767, JP-A-4-13774, JP-A-4-89287, JP-A-7-175187, JP-A-10-60296, JP-A-11-78258. Can be synthesized with reference to conventionally known methods described in JP-A Nos. 2004-13834 and 2006-350300.

  These dyes may be used alone or in combination of two or more. The content of the pigment is preferably 0.5 to 15% by mass and more preferably 1 to 10% by mass with respect to the whole toner.

[Metal compounds]
The metal compound according to the present invention is a compound represented by the following general formula (2).

In the general formula (2),
M is a divalent metal,
R ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
R ₂ is a hydrogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a halogen atom, or a cyano group,
R ₃ is a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms.

  The compound represented by the general formula (2) can also be represented by using the limiting structural formulas of the following general formula (2a) and the following general formula (2b). In the present invention, the compound represented by the general formula (2), the compound represented by the following general formula (2a), and the compound represented by the following general formula (2b) are essentially the same, and are distinguished from each other. Not. The distinction between a covalent bond (indicated by −) and a coordination bond (indicated by...) Is also a formal one and does not represent an absolute distinction.

In the general formulas (2a) and (2b), M, R ₁ , R ₂ , and R ₃ are groups having the same meaning as in the general formula (2).

The metal compound in the present invention is preferably obtained by synthesizing a compound represented by the following general formula (2-1) and then reacting with a divalent metal compound. The method for synthesizing this metal compound can be synthesized according to the method described in “Chelate Chemistry (5) Complex Chemistry Experimental Method [I] (Edited by Minami Edo)”. Examples of the divalent metal compound used include copper (II) chloride, copper (II) acetate, copper perchlorate, magnesium chloride, and magnesium acetate. The metal compounds used in the present invention may have a neutral ligand according to the central metal, representative ligands include H 2 _O or NH _3.

In the general formula (2-1), R ₁ , R ₂ , and R ₃ are groups having the same meaning as in the general formula (2).

  In general formula (2), general formula (2a), and general formula (2b), M is a divalent metal. Specific examples of the metal include, for example, magnesium (Mg), calcium (Ca), nickel (Ni), copper (Cu), cobalt (Co), zinc (Zn), iron (Fe), palladium (Pd). Platinum (Pt) and the like.

In General Formula (2), General Formula (2a), General Formula (2b), and General Formula (2-1), R ₁ is a substituted or unsubstituted straight chain having 1 to 20 carbon atoms, A branched or cyclic alkyl group. Specific examples of the alkyl group are the same as the alkyl groups that can be used for Rx ₁ and Rx ₂ in the general formula (1) in the section of the colorant, and thus detailed description thereof is omitted here.

  One or more hydrogen atoms of the alkyl group may be substituted with a substituent. Examples of the substituent include alkenyl groups (eg, vinyl group, allyl group, etc.), alkynyl groups (eg, ethynyl group, propargyl group, etc.), aryl groups (eg, phenyl group, naphthyl group, etc.), heteroaryl groups (For example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, etc.) Heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group) , Cyclopentyloxy group, cyclohexyloxy Group), aryloxy group (for example, phenoxy group, naphthyloxy group, etc.), alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, cyclopentylthio group, cyclohexyl) Thio group etc.), arylthio group (eg 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 (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminos) Phonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, Acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, 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 groups (eg, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octyl) Carbonylamino group, dodecylcarbonylamino 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, phenylamino Carbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthyl group) Ureido 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 (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group) Group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, Butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc., cyano group, nitro group, halogen atom (for example, chlorine atom, bromine atom, fluorine) Atoms, iodine atoms, etc.), and these groups may be further substituted with the same groups.

R ₁ is preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, more preferably a substituted or unsubstituted linear alkyl group having 1 to 4 carbon atoms. More preferably, they are a methyl group, a trifluoromethyl group, or an ethyl group, and particularly preferably a methyl group or a trifluoromethyl group.

R ₂ is a hydrogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a halogen atom, or a cyano group. More specifically, an alkoxycarbonyl group such as a methyloxycarbonyl group, an ethyloxycarbonyl group, a butyloxycarbonyl group, an octyloxycarbonyl group or a dodecyloxycarbonyl group; an aryloxycarbonyl such as a phenyloxycarbonyl group or a naphthyloxycarbonyl group Group: aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group Sulfamoyl groups such as 2-pyridylaminosulfonyl group; methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexyl Rusulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group and other sulfinyl groups; methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2- Alkylsulfonyl groups such as ethylhexylsulfonyl group and dodecylsulfonyl group; arylsulfonyl groups such as phenylsulfonyl group, naphthylsulfonyl group and 2-pyridylsulfonyl group; acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group Octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl Boniru acyl groups such as a halogen atom (e.g., chlorine atom, bromine atom, a fluorine atom, an iodine atom), a cyano group.

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

R ₃ is a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms.

Here, the aromatic hydrocarbon structure-containing group having 9 to 120 carbon atoms means that the total number of carbon atoms in R ₃ is 9 to 120, and an aromatic hydrocarbon structure at an arbitrary position in R ₃ Refers to a group containing Examples of the aromatic hydrocarbon structure include an aryl group (for example, a phenyl group, a naphthyl group, etc.). For example, when the aromatic hydrocarbon structure is a phenyl group, an arbitrary substituent having 3 or more carbon atoms is further included. Together with this, R ₃ is formed. In this case, it may have 3 or more substituents having 1 carbon atom, and may have 1 or more substituents each having 1 carbon atom and 2 substituents having 2 carbon atoms. The total number of carbon atoms in R ₃ is preferably 9 to 40, more preferably 12 to 40, and still more preferably 14 to 30.

R ₃ is preferably a group represented by the following general formula (3).

In the general formula (3), L represents a linear or branched alkylene group having 1 to 15 carbon atoms, —SO ₂ O—, —OSO ₂ —, —SO ₂ —, —CO—, —O. _{-, - S -, - SO} 2 NH -, - NHSO 2 -, - CONH -, - NHCO -, - COO-, and divalent alone or in combination with it based on the linking group selected from -OOC- the stands, * in, bound to the oxygen atom adjacent to R ₃ in the general formula (2).

  Specific examples of the linear or branched alkylene group having 1 to 15 carbon atoms include, for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a propylene group, an ethylethylene group, a pentamethylene group, and a hexamethylene group. Group, 2,2,4-trimethylhexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group Etc.

L may have a substituent, and examples of the substituent include the same groups as the substituent used in R ₁ of the general formula (2).

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

R ₄ represents an aryl group (for example, a phenyl group, a naphthyl group, etc.).

  Although the more specific example of the bivalent coupling group represented by L below is shown, this invention is not limited to these.

L is bonded to an oxygen atom adjacent to R ₃ in the general formula (2) or R ₄ in *.

R ₃ and R ₄ may have a substituent, and examples of the substituent include the same groups as the substituent used in R ₁ of the general formula (2).

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

R ₄ is preferably a phenyl group, more preferably a phenyl group having a substituent, and further preferably a phenyl group having an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, or an amide group. Particularly preferred is a phenyl group having an alkyl group or an alkoxy group.

Preferable specific examples of R ₄ include groups represented by the following general formulas (1) -1 to (1) -20. R ₄ is bonded to the linking group represented by L in *. In the following chemical formula, (n) means a normal alkyl group.

R ₃ or the general formula (3) is more preferably a group represented by the following general formula (3-1).

In the general formula (3-1), L and * represent a group having the same meaning as L and * in the general formula (3), and R ₅ is a linear or branched group having 8 to 30 carbon atoms. Represents an alkyl group, and n represents an integer of 1 to 3.

R ₅ is preferably an alkyl group having 12 to 24 carbon atoms, and more preferably an alkyl group having 16 to 24 carbon atoms. R ₅ may have a substituent, and examples of the substituent include a group having the same meaning as the substituent used in R ₁ of the general formula (2). R ₅ is preferably a linear alkyl group, and more preferably composed of only carbon atoms and hydrogen atoms.

  n is preferably 1 or 2, more preferably 1.

  Specific examples of the metal compound represented by the general formula (2) are shown below. In addition, although the following specific example has shown the compound whose M of General formula (2) is Cu, even if it is a compound by which M was replaced with another bivalent metal, it is used by this invention. Examples of the metal compound are the same.

  These metal compounds may be used alone or in combination of two or more. The content of the metal compound is preferably 0.5 to 10% by mass and more preferably 1 to 8% by mass with respect to the whole toner.

  The colorant used in the present invention may be used in combination with other colorants. As the colorant that can be used in combination with the pigment or the metal compound, generally known dyes can be used, and oil-soluble dyes are particularly preferable.

  It is also possible to use a quinacridone pigment in combination. Specific examples of the quinacridone pigment include C.I. I. Dimethylquinacridone pigments such as CI Pigment Red 122; I. Pigment red 202, C.I. I. Dichloroquinacridone pigments such as CI Pigment Red Red 209; I. Examples thereof include unsubstituted quinacridone such as CI Pigment Violet 19, and a mixture or solid solution of at least two pigments selected from these pigments. The pigment may be a dry pigment in the form of powder, granule or block, or may be a wet cake or a slurry. Among the quinacridone pigments, C.I. I. Pigment Red 122 is preferable.

[External additive]
The external additive used in the present invention includes silica particles (hereinafter, also simply referred to as large-diameter silica) formed by a sol-gel method and having a volume average primary particle diameter of 60 to 150 nm.

  The large diameter silica of the present invention can be formed by a sol-gel method. Silica particles produced by the sol-gel method have a larger particle size and a uniform particle size (narrow particle size distribution, ie, monodisperse) compared to fumed silica obtained by a general production method. It is. The narrower the particle size distribution of the silica particles, the more the external additive can be fixed on the surface of the binder resin during mixing, and the rate at which the external additive is detached can be reduced.

  When the volume average primary particle diameter of the large-diameter silica is less than 60 nm, a sufficient distance between the toner particles cannot be ensured, and the toner tends to form soft aggregates and image fogging is likely to occur. On the other hand, when the volume average primary particle diameter of the large-diameter silica exceeds 150 nm, the external additive is not sufficiently fixed on the surface of the binder resin, and the external additive tends to be detached or unevenly distributed. The volume average primary particle diameter of the large-diameter silica is preferably 80 to 120 nm. By setting the volume average primary particle diameter of the large-diameter silica within the range of the present invention, the large-diameter silica is sufficiently fixed to the surface of the binder resin, the contact between the toners is relaxed, and the soft agglomerates of the toner are hardly formed. The chargeability of the toner, the adhesive force between the toner particles and the photosensitive member, or the adhesive force between the toner particles and the intermediate transfer member can be controlled within a desired range. Therefore, fog can be reduced.

  In the present specification, the volume average primary particle diameter of the large-diameter silica was measured as follows using “Laser diffraction / scattering particle size distribution analyzer LA-750” (manufactured by Horiba, Ltd.).

  After adding large diameter silica to methanol so that methanol: large diameter silica = 1: 0.005 by mass ratio, the large diameter silica was dispersed in methanol by an ultrasonic irradiator. The particle size distribution of the large-diameter silica thus treated was measured with “Laser diffraction / scattering particle size distribution analyzer LA-750” (manufactured by Horiba, Ltd.), and the average particle size was determined. The average particle diameter thus determined is a so-called volume average particle diameter. In addition, the average particle diameter of the large-diameter silica was measured using an electron microscope, and compared with the average particle diameter obtained from the measurement result by the above-mentioned apparatus, it was confirmed that these values matched, and the By confirming that the large-diameter silica was not aggregated, it was determined that the average particle diameter was that of primary particles.

  The standard deviation of the volume average primary particle diameter can be determined simultaneously with the average particle diameter when measured with “LA-750”.

  The large-diameter silica produced by the sol-gel method is produced by hydrolysis of a hydrocarbyloxysilane compound (such as an alkoxysilane compound or a phenoxysilane compound). Specific examples include the following procedures.

(1) Using ammonia as a catalyst, a tetraalkoxysilane such as tetramethoxysilane or tetraethoxysilane is dropped into a mixed solvent of water and alcohol while stirring and reacted. An aqueous suspension of silica particles is thus formed:
(2) An aqueous suspension of silica particles is added to a silane coupling agent such as methyltrimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane, hexamethyldisilazane (HMDS), methyltrimethoxysilane, and isobutyltrimethoxy. Hydrophobic treatment of the silica particle surface is performed by sequentially adding a hydrophobizing agent such as silane:
(3) The target large-diameter silica is obtained by removing the solvent from the hydrophobized silica sol and drying.

  The volume average primary particle size of the large-diameter silica produced by the sol-gel method is such as the amount of addition of the hydrocarbyloxysilane compound, ammonia, alcohol, water and other compounds as raw materials during hydrolysis, reaction temperature, stirring rate, supply rate, etc. The desired particle size can be controlled by the control.

  In the external additive according to the present invention, known inorganic fine particles, organic fine particles, lubricants, and the like may be used in combination with the above large-diameter silica from the viewpoint of improving fluidity and cleaning properties.

  As the inorganic fine particles, conventionally known ones can be used. For example, silica, titania (titanium dioxide), alumina, strontium titanate, barium titanate, titanic acid having a number average primary particle diameter of 5 to 300 nm. There are titanic acid compound particles such as calcium. In addition, these external additives may be hydrophobized with a silane coupling agent, a titanium coupling agent, a higher fatty acid, silicone oil, or the like from the viewpoint of environmental stability and heat-resistant storage stability.

  Further, as the organic fine particles, specifically, as specific examples of the organic fine particles, for example, polymers such as polystyrene, polymethyl methacrylate, styrene-methyl methacrylate copolymer having a number average primary particle size of 10 to 2000 nm are available. is there. Furthermore, specific examples of the lubricant include aluminum stearate and zinc stearate.

  The ratio of the large-diameter silica in the external additive is preferably 10 to 100% by mass, and more preferably 25 to 100% by mass with respect to the entire external additive.

  The addition amount of these external additives and lubricants is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, based on the total mass of the toner.

[Release agent]
The toner for developing an electrostatic image of the present invention can contain a release agent. Specific examples of the release agent include the following.

(1) Polyolefin waxes such as polyethylene wax and polypropylene wax (2) Long chain hydrocarbon waxes such as paraffin wax, sazol wax and microcrystalline wax (3) Dialkyl ketone waxes such as distearyl ketone (4) Carna Uba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetramyristate, pentaerythritol tetrastearate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, behenyl behenate, glycerin tribehenate , 1,18-octadecanediol distearate, tristearyl trimellitic acid, ester wax such as distearyl maleate (5) ethylenediamine di Amide waxes such as behenyl amide and trimellitic acid tristearyl amide.

  40-125 degreeC is preferable, as for melting | fusing point of the said mold release agent, 50-120 degreeC is more preferable, and 60-90 degreeC is further more preferable. The above releasing agents can be used alone or in combination of two or more. Among the above releasing agents, paraffin wax, microcrystalline wax, or behenyl behenate is preferable.

  By using a release agent having a melting point in the above range, the heat resistant storage stability of the toner can be ensured. Also, when performing so-called low-temperature fixing in which a toner image is fixed at a lower temperature than in the past, image formation can be performed without causing a cold offset or the like. The addition amount of the release agent is preferably 1 to 30% by mass and more preferably 5 to 20% by mass with respect to the whole toner. By setting the addition amount of the release agent within the above range, smooth separation characteristics can be obtained during fixing and the transparency of the toner image can be maintained.

[Charge control agent]
A known charge control agent can be added to the toner for developing an electrostatic image according to the present invention. The charge control agent is not particularly limited, and as the negative charge control agent, a colorless, white, or light color charge control agent that does not affect the color tone or translucency of the toner image can be used. Specific examples of the negative charge control agent include salicylic acid derivative metals, calixarene compounds, organic boron compounds, and fluorine-containing quaternary ammonium salt compounds. The addition amount of the charge control agent is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5.0 parts by mass with respect to 100 parts by mass of the binder resin.

  Examples of the salicylic acid derivative metal include those described in JP-A Nos. 53-127726 and 62-145255. Examples of the calixarene compound include those described in JP-A-2-201378. Examples of the organic boron compound include those described in JP-A-2-221967. Examples of the fluorine-containing quaternary ammonium salt compound include those described in JP-A-3-1162.

[Image stabilizer]
The toner for developing an electrostatic charge image of the present invention may contain an image stabilizer in order to improve image storage stability. As the image stabilizer, for example, in addition to the compounds described in JP-A-8-29934, commercially available image stabilizers composed of phenolic, amine-based, sulfur-based, and phosphorus-based compounds can also be used. Further, for the same purpose, an ultraviolet absorber can be added, and a known organic ultraviolet absorber or inorganic ultraviolet absorber can be added.

  Examples of organic ultraviolet absorbers include the following.

(1) benzotriazole compounds; 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole (2) Benzophenone compounds; 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, etc. (3) Phenyl salsylate compounds; phenyl salsylate, 4-t-butylphenyl (4) Hydroxybenzoate compounds; 2,5-t-butyl-4-hydroxybenzoic acid n-hexadecyl ester, 2,4-di-t-butylphenyl-3 ′, 5′-di- t-butyl-4′-hydroxybenzoate and the like.

  Examples of inorganic ultraviolet absorbers include titanium oxide, zinc oxide, cerium oxide, iron oxide, and barium sulfate.

  Of organic ultraviolet absorbers and inorganic ultraviolet absorbers, organic ultraviolet absorbers are preferred. Further, the ultraviolet absorber preferably has a 50% transmittance wavelength of 350 to 420 nm, more preferably 360 to 400 nm. A toner having a 50% transmittance wavelength in the above range reliably exhibits an ultraviolet shielding ability, and even if an ultraviolet absorber is added, there is no influence of coloring. 10-200 mass% is preferable with respect to a pigment | dye, and, as for the addition amount of a ultraviolet absorber, 50-150 mass% is more preferable.

[Method for producing toner for developing electrostatic image]
Next, a method for producing an electrostatic charge image developing toner according to the present invention will be described. The method for producing the toner for developing an electrostatic charge image according to the present invention is not particularly limited, and is a pulverization method, suspension polymerization method, miniemulsion polymerization aggregation method, emulsion polymerization aggregation method, dissolution suspension method, polyester molecular elongation. And other known methods. Among these, the miniemulsion polymerization aggregation method is preferable.

  In the miniemulsion polymerization aggregation method, a toner is prepared by the following procedure. That is, a polymerizable monomer solution in which a release agent is dissolved in an aqueous medium in which a surfactant is dissolved so as to have a concentration equal to or lower than the critical micelle concentration, and oil droplets of 10 to 1000 nm using mechanical energy. A dispersion is formed. A water-soluble radical polymerization initiator is added to the obtained dispersion to perform polymerization, thereby forming binder resin particles. Then, the formed binder resin particles are aggregated and the particles are fused to produce toner particles.

  The reason why the mini-emulsion polymerization aggregation method is preferable is that the polymerization is performed in oil droplets, so that a state in which the release agent particles are surely included in the binder resin can be formed in the toner particles. As a result, since the vapor does not generate a vaporizing component from the release agent until the toner is heated by the fixing device, the performance of the release agent is not deteriorated.

  In the miniemulsion polymerization aggregation method, polymerization is carried out by adding an oil-soluble radical polymerization initiator together with the water-soluble radical polymerization initiator to the monomer solution described above instead of adding the water-soluble radical polymerization initiator. It can also be done.

  When the resin particles are formed by the miniemulsion polymerization aggregation method, the resin particles having a structure of two or more layers made of binder resins having different compositions can be formed. In this case, a polymerization initiator and a polymerizable monomer are added to the dispersion of the first resin particles prepared by a conventional miniemulsion polymerization process (first stage polymerization), and the system is polymerized (second stage polymerization). ) In this way, resin particles having a two-layer structure can be formed. And the resin particle of a multilayered structure can be formed by repeating this 2nd step polymerization.

The toner production method by the miniemulsion polymerization aggregation method is performed by the following procedure, for example. That is,
(1) Dissolving / dispersing step of preparing a polymerizable monomer solution by dissolving or dispersing a releasing agent and, if necessary, a toner particle constituent material such as a charge control agent in a polymerizable monomer serving as a binder resin. (2) Dispersion preparation step of preparing a dye particle dispersion and a metal compound dispersion by dispersing a dye and a metal compound in an aqueous medium, respectively. (3) Making the polymerizable monomer solution into oil droplets in an aqueous medium. , Polymerization step of preparing a binder resin particle dispersion by the miniemulsion method (4) agglomeration in which the binder resin particles, the dye, and the metal compound are aggregated and fused in an aqueous medium to form aggregated particles. Fusing process (5) Aging process for adjusting the shape by aging the agglomerated particles with thermal energy to produce a toner particle dispersion (6) Cooling process for cooling the toner particle dispersion (7) Cooled toner particle dispersion More tona Filtration / washing process for solid-liquid separation of particles and removal of surfactants from toner particle surfaces (8) Drying process for drying washed toner particles (9) Adding external additive to dried toner particles External processing step to be added.

  Hereinafter, each step will be described.

(1) Dissolution / Dispersion Step This step is a step of preparing a polymerizable monomer solution by dissolving or dispersing toner particle constituent materials such as a release agent and a charge control agent in a polymerizable monomer.

  In this polymerizable monomer solution, it is possible to add at least one of a polymerization initiator described later and other oil-soluble components.

(2) Dispersion Preparation Step In this dispersion preparation step, a dye, a metal compound, and if necessary, a quinacridone pigment are dispersed in an aqueous medium, a dye particle dispersion, a metal compound dispersion, and, if necessary, It is a step of preparing each quinacridone pigment dispersion.

  These pigment particle dispersions and the like can be prepared by dispersing pigments and the like in an aqueous medium. The dispersion treatment of the pigment, the metal compound, etc. is carried out in a state where the surfactant concentration is set to a critical micelle concentration (CMC) or more in water. The disperser used for the dispersion treatment is not particularly limited, and an ultrasonic disperser, a mechanical homogenizer, a pressure disperser such as Manton Gorin or a pressure homogenizer, a media type disperser such as a sand grinder, a Getzmann mill, a diamond fine mill, or the like. Can be used.

  As the dye and the metal compound, those whose surface is modified can be used. Specifically, the pigment and the metal compound are dispersed in a solvent, and a reaction treatment is performed by adding a surface modifier to the dispersion and heating the system. After completion of the reaction, the dye and the metal compound are separated by filtration, washed and filtered with the same solvent, and then dried to obtain the dye treated with the surface modifier.

(3) Polymerization step This polymerization step is a step of forming binder resin particles containing a release agent and a binder resin. In the polymerization step, for example, the polymerizable monomer solution is added to an aqueous medium containing a surfactant having a concentration equal to or lower than the critical micelle concentration, mechanical energy is added to form oil droplets, and then water-soluble By adding a radical polymerization initiator, the polymerization reaction is carried out in the oil droplets. In addition, when forming the resin particle of a multilayer structure, it can form by adding the resin particle used as a nucleus particle in an aqueous medium, and performing a polymerization reaction.

  The binder resin particles formed in the polymerization step may be colored or uncolored. The colored binder resin particles are formed by polymerizing a monomer composition containing a pigment and a metal compound. When forming binder resin particles that are not colored, add pigment particle dispersion, metal compound dispersion, and, if necessary, quinacridone pigment dispersion to the binder resin particle dispersion in the aggregation process described later. Thus, the toner particles can be formed by aggregating the binder resin particles and the pigment.

  Here, the “aqueous medium” means that the main component (50% by mass or more) is made of water. That is, it refers to a dispersion medium composed of 50 to 100% by mass of water and 0 to 50% by mass of a water-soluble organic solvent. Examples of water-soluble organic solvents that are components other than water include the following. For example, there are methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, tetrahydrofuran and the like. Among these, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol that do not dissolve the resin are particularly preferable.

  The method for dispersing the polymerizable monomer solution in the aqueous medium is not particularly limited, but a method of dispersing by adding mechanical energy is preferred. A dispersion apparatus for dispersing oil droplets by applying mechanical energy is not particularly limited. For example, “CLEAMIX (registered trademark)”, an ultrasonic dispersion machine, a mechanical homogenizer, a manton gourin, and a pressure homogenizer Etc. Moreover, 10-1000 nm is preferable and, as for the dispersed particle diameter of a polymerizable monomer solution, 30-300 nm is more preferable.

(4) Aggregation / fusion process In the aggregation / fusion process, the binder resin particles formed in the polymerization process are aggregated and fused in an aqueous medium. In the aggregation / fusion process, if the binder resin particles are not colored, add a pigment particle dispersion, a metal compound dispersion, and, if necessary, a quinacridone pigment dispersion to the binder resin particle dispersion. Then, the binder resin particles and the pigment are aggregated and fused. Aggregation can be performed by adding a dispersion of binder resin particles having different resin compositions in the middle of the aggregation / fusion process.

  In the agglomeration / fusion process, it is also possible to add internal additive particles such as a charge control agent together with the binder resin particles and the dye to cause aggregation and fusion.

  A preferred agglomeration / fusion method is to add a flocculant composed of an alkali metal salt, a salt of a Group 2 element, or the like into an aqueous medium in which binder resin particles and pigments are present, so that these particles are added. Agglomerate. Next, the fusion resin is heated to a temperature equal to or higher than the glass transition temperature of the binder resin particles and equal to or higher than the melting peak temperature of the release agent, and the fusion proceeds simultaneously with the aggregation.

  In this aggregation / fusion process, it is necessary to quickly raise the temperature by heating, and the temperature raising rate is preferably 1 ° C./min or more. The upper limit of the rate of temperature increase is not particularly limited, but coarse particles may be generated due to rapid agglomeration and fusion, so that it is preferably 15 ° C./min or less from the viewpoint of suppressing this.

  Furthermore, after the dispersion liquid of the binder resin particles and the dye reaches a temperature not lower than the glass transition temperature and not lower than the melting peak temperature of the release agent, the temperature of the dispersion liquid is maintained for a certain period of time for aggregation and fusion. It is important to continue. In this way, by maintaining the dispersion temperature for a certain period of time, toner particle growth (aggregation of binder resin particles and colorant) and fusion (disappearance at the interface between the particles) proceed effectively and finally. The durability of the obtained toner can be improved.

(5) Aging process Specifically, this aging process is carried out by heating and stirring the system containing the aggregated particles, so that the heating temperature, the stirring speed, and the heating time are changed until the aggregated particles have a desired average circularity. This is a step of controlling and adjusting to form toner particles having a desired shape. In this aging step, it is preferable to control the shape of the toner particles by thermal energy (heating).

  In this ripening step, a binder resin particle dispersion is further added to the toner particle dispersion to attach and fuse the binder resin particles to the surface of the toner particles, thereby forming toner particles called a so-called core-shell structure. It is good also as what to do. In this case, it is preferable that the glass transition point of the binder resin particles forming the shell be 20 ° C. or more higher than the glass transition point of the binder resin particles constituting the core.

  Further, the binder resin particles used in the aggregation / fusion step are a resin (hydrophilic resin) made of a polymerizable monomer having an ionic dissociation group as a raw material and a polymerizable monomer having no ionic dissociation group In the case where it is configured to contain only a resin (hydrophobic resin) made from only the raw material, in this aging step, the hydrophilic resin is oriented on the surface side of the aggregated particles, and the hydrophobic resin is oriented on the inside side of the aggregated particles. Toner particles having a core-shell structure can be formed.

(6) Cooling step This cooling step is a step of cooling the toner particle dispersion. The cooling rate during the cooling treatment is preferably 1 to 20 ° C./min. The cooling treatment method is not particularly limited, and examples thereof include known methods such as a method of cooling by introducing a refrigerant from the outside of the reaction vessel, and a method of cooling by directly introducing cold water into the reaction system.

(7) Filtration / washing step In this filtration / washing step, a filtration step of separating the toner particles from the toner particle dispersion that has been cooled to a predetermined temperature in the cooling step, followed by filtration, and toner particles called wet cake It comprises a washing step of removing deposits such as surfactants and aggregating agents, alkalis used in the ripening step, and the like from the surface of the toner particles that have been filtered and processed in the form of aggregates.

  In the washing step, water washing is performed until the electrical conductivity of the filtrate reaches a level of 5 to 10 μS / cm. In the filtration step, solid-liquid separation is performed by a known filtration method such as a centrifugal separation method, a vacuum filtration method using Nutsche or the like, or a filtration method using a filter press or the like.

(8) Drying Step This drying step is a step of drying the wet cake that has been subjected to the cleaning treatment to produce dried toner particles. Dryers used in this process include airflow dryers, spray dryers, vacuum freeze dryers, vacuum dryers, etc., stationary shelf dryers, mobile shelf dryers, fluidized bed dryers, rotary dryers An agitator, a stirrer dryer, or the like can also be used. The moisture content of the dried toner particles is preferably 5% by mass or less, and more preferably 2% by mass or less. In addition, when the toner particles that have been dried are aggregated due to weak interparticle attraction, the aggregate may be crushed. Examples of the crushing treatment apparatus include mechanical crushing apparatuses such as a jet mill, a Henschel mixer, a coffee mill, and a food processor.

(9) External Addition Processing Step This step is a step of adding an external additive to the dried toner particles as necessary. As a mixing device for adding an external additive, there is a mechanical mixing device such as a Henschel mixer or a coffee mill.

  Through the above procedure, the toner according to the present invention can be produced by the miniemulsion polymerization aggregation method.

  Hereinafter, the surfactant, the polymerization initiator, the chain transfer agent, and the flocculant used in the toner production method such as the above-described miniemulsion polymerization aggregation method will be described.

[Surfactant]
When the toner according to the present invention is produced by the suspension polymerization method or the above-described miniemulsion polymerization aggregation method or emulsion polymerization aggregation method, a surfactant is added to an aqueous medium to produce a binder resin or aggregated particles. The surfactant used in these polymerization methods is not particularly limited, but the following ionic surfactants are preferable.

(1) Sulfonate salt; sodium dodecylbenzene sulfonate, sodium arylalkyl polyether sulfonate (2) sulfate ester salt; sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium lauryl sulfate, etc. (3) Fatty acid salts; sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate and the like.

  Moreover, the nonionic surfactants listed below can also be used. That is, polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, ester of polyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, ester of higher fatty acid and polyethylene glycol, ester of higher fatty acid and polypropylene oxide, And sorbitan esters.

(Polymerization initiator)
When the toner used in the present invention is prepared by the suspension polymerization method or the above-described miniemulsion polymerization aggregation method or emulsion polymerization aggregation method, the binder resin is obtained by polymerizing a polymerizable monomer using a radical polymerization initiator. Form.

  When the resin is formed by the suspension polymerization method, an oil-soluble radical polymerization initiator can be used. Specific examples of the oil-soluble polymerization initiator include the following.

(1) Azo or diazo polymerization initiator; 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane- 1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, etc. (2) peroxide polymerization initiator; benzoyl peroxide, methyl ethyl ketone peroxide , Diisopropylperoxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis- ( 4,4-t-butylperoxycyclohexyl) propane, tris- Polymeric initiator having a side chain t- butylperoxy) triazine (3) a peroxide.

  In the case where the binder resin is formed by the miniemulsion polymerization aggregation method or the emulsion polymerization aggregation method, a water-soluble radical polymerization initiator can be used. Examples of the water-soluble radical polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and salts thereof, and hydrogen peroxide.

[Chain transfer agent]
When the toner used in the present invention is produced by suspension polymerization, the above-described miniemulsion polymerization aggregation method or emulsion polymerization aggregation method, a known chain transfer agent may be used to adjust the molecular weight of the binder resin. it can. Specific chain transfer agents include n-octyl mercaptan, n-decyl mercaptan, mercaptans such as tert-dodecyl mercaptan, n-octyl-3-mercaptopropionic acid ester, terpinolene, carbon tetrabromide, α-methylstyrene dimer Etc.

[Flocculant]
When the toner according to the present invention is produced by the miniemulsion polymerization aggregation method or the emulsion polymerization aggregation method, an aggregating agent is used for aggregating the resin particles. Examples of the flocculant include alkali metal salts and alkaline earth metal salts. Examples of the alkali metal that constitutes the flocculant include lithium, potassium, and sodium, and examples of the alkaline earth metal that constitutes the flocculant include magnesium, calcium, strontium, and barium. Of these, potassium, sodium, magnesium, calcium, and barium are preferable. Examples of the alkali metal or alkaline earth metal counter ion (anion constituting the salt) include chloride ion, bromide ion, iodide ion, carbonate ion, sulfate ion, etc. [Developer]
When the toner used in the present invention is used as a developer, it may be used as a one-component developer or a two-component developer.

  When used as a one-component developer, a non-magnetic one-component developer or a magnetic one-component developer containing magnetic particles in the toner can be used, and any of them can be used.

  The carrier used when used as a two-component developer is not particularly limited, and a known carrier can be used. Specifically, resin-coated carriers described in JP-A Nos. 62-39879 and 56-11461 are preferable.

  Here, the resin-coated carrier will be described. The volume-based median diameter of the carrier is preferably 20 to 80 μm, and more preferably 25 to 35 μm from the viewpoint of obtaining good image quality and improving filming resistance. Further, ferrite, magnetite granulated material, and the like can be used as the core particles constituting the resin-coated carrier, and ferrite is preferred among them. Among the known ferrite compositions, manganese-magnesium-strontium ferrite is preferable from the viewpoint of preventing carrier adhesion.

  As the coating resin constituting the resin-coated carrier, a polymer resin using the following polymerizable monomer alone or a copolymer resin formed using two or more of the following polymerizable monomers is used.

(1) Styrenes; styrene, α-methylstyrene, etc. (2) α-methylene fatty acid monocarboxylic acids; methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methacrylic acid Methyl, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc. (3) Nitrogen-containing acrylics; dimethylaminoethyl methacrylate, etc. (4) Vinylpyridines; 2-vinylpyridine, 4-vinylpyridine, etc. (5) ) Vinyl nitriles; acrylonitrile, methacrylonitrile, etc. (6) Vinyl ethers; Vinyl methyl ether, vinyl isobutyl ether, etc. (7) Vinyl ketones; Vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone, etc. Ethylene, propylene, etc. (9) Vinyl-based fluorine-containing monomers; vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, etc. Also, silicone resins including methylsilicone and methylphenylsilicone, polyester resins including bisphenol, glycol, etc. Resins such as epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and polycarbonate resins can also be used.

  The above resins can be used alone or in combination of two or more to form a coating resin. Among them, styrene / cyclohexyl methacrylate copolymer resin (copolymerization ratio = 5: 5 to 9: 1) is preferable from the viewpoint of the humidity dependency of charging. From the same viewpoint, a combination of about 50% perfluoroacrylate is also preferred.

  Further, from the viewpoint of preventing wear of the resin coating layer, polymethyl methacrylate particles or melamine resin particles having a number average particle diameter of 0.1 to 0.3 μm may be added. Furthermore, from the viewpoint of improving the development characteristics, carbon black, graphite, titanium oxide, aluminum oxide or the like can be added to the resin coating layer in an amount of about 5 to 30% by mass.

  The coating amount of the coating resin is preferably in the range of 0.1 to 10 parts by mass and more preferably in the range of 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the core particles. . The mixing ratio between the toner and the carrier constituting the two-component developer can be appropriately selected according to the purpose.

[Physical properties of toner]
The toner according to the present invention preferably has a particle size in the range of 3 μm or more and 8 μm or less in terms of volume-based median diameter (D ₅₀ ). The volume-based median diameter of the toner is measured using, for example, a measuring apparatus in which a computer system for data processing (Beckman Coulter, Inc.) is connected to “Coulter Multisizer 3 (Beckman Coulter, Inc.)”. Can be calculated. Specifically, 0.02 g of toner is added to 20 ml of a surfactant solution (for example, a surfactant solution obtained by diluting a neutral detergent containing a surfactant component 10 times with pure water for the purpose of dispersing the toner). After being conditioned, ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion. This toner dispersion is injected into a beaker containing “ISOTON II (manufactured by Beckman Coulter, Inc.)” in a sample stand with a pipette until the display density of the measuring device becomes 8%. Here, by using this concentration, a reproducible measurement value can be obtained. Then, in the measurement apparatus, the measurement particle count is set to 25,000, the aperture diameter is set to 50 μm, and the frequency value obtained by dividing the measurement range of 1 to 30 μm into 256 parts is calculated. The particle diameter of 50% from the largest is defined as the volume-based median diameter.

  In the toner of the present invention, the coefficient of variation (CV value) in the volume-based particle size distribution is preferably in the range of 5% to 30%, particularly in the range of 10% to 25%. It is preferable. The coefficient of variation (CV value) in the volume-based particle size distribution is 100 times the value obtained by dividing the standard deviation of the number particle size distribution of toner particles by the volume-based median diameter, and is calculated by the following equation (1). The coefficient of variation (CV value) means that the smaller the value is, the sharper the particle size distribution is, that is, the toner particles have the same size.

  By setting the coefficient of variation CV value in the volume-based particle size distribution within the above range, the toner particles have uniform sizes, and variations in melting characteristics among the toner particles can be suppressed. Therefore, since the toner image can be melted and fixed without unevenness at the time of fixing, a clear toner image having a high chroma color tone expressed by the combination of the dye and the metal compound described above can be reliably formed.

  The toner according to the present invention preferably has an average circularity value represented by the following formula (2) in the range of 0.930 to 1.000 from the viewpoint of improving the transfer efficiency of individual toner particles. 0.940 to 0.995 is more preferable.

  The toner of the present invention preferably has a softening point temperature (Tsp) of 70 ° C. or higher and 130 ° C. or lower, and more preferably 70 ° C. or higher and 120 ° C. or lower. By setting the softening point temperature within the above range, the influence of heat applied to the toner at the time of fixing can be reduced, and an image can be formed without applying a thermal load to toner components such as a colorant. As a result, since there is no possibility that the colorant is deteriorated by the influence of heat, it is possible to reliably form a vivid color image with a wide color reproduction region.

The softening point temperature of the toner can be controlled by combining, for example, the following methods. That is,
(1) Adjusting the type and composition ratio of the polymerizable monomer that forms the binder resin. (2) In the toner production process, for example, a chain transfer agent is used in the process of forming the binder resin. Adjusting the molecular weight of the binder resin according to the type and amount of the transfer agent (3) Adjusting the type and amount of the constituent material such as the release agent These methods (1) to (3) are appropriately combined. Thus, the softening point temperature can be controlled.

The softening point temperature of the toner can be measured using, for example, “Flow Tester CFT-500 (manufactured by Shimadzu Corporation)”. Specifically, a cylindrical body having a height of 10 mm is formed using toner, and a pressure of 1.96 × 10 ⁶ Pa is applied by a plunger while heating the cylindrical body at a temperature rising rate of 6 ° C./min. To soften. Then, the softened material is pushed out from a nozzle having a diameter of 1 mm and a length of 1 mm to create a softening flow curve indicating the relationship between the amount of descent from the plunger and the temperature. From this softening flow curve, the temperature at a drop of 5 mm is defined as the softening point temperature.

[Image forming method]
The image forming method using the toner of the present invention includes, for example, at least the following steps. That is,
(1) An electrostatic latent image forming step for forming an electrostatic latent image on an electrostatic latent image carrier (photoconductor). (2) Using the developer containing the toner according to the present invention, an electrostatic latent image is formed. Developing process for developing a toner image by developing an electrostatic latent image formed on an image carrier (3) Transfer for transferring a toner image formed on an electrostatic latent image carrier onto a transfer body such as paper Step (4) A fixing step of fixing the toner image transferred onto the transfer body.

  In addition, you may have other processes other than the said 4 processes. For example, it is preferable to have a cleaning step of removing the toner remaining on the surface of the electrostatic latent image carrier after transferring the toner image. In the transfer step, the toner image may be transferred from the electrostatic latent image carrier onto the recording medium via an intermediate transfer member.

  Regarding the image forming apparatus, the fixing method, the fixing apparatus, and the like that realize the image forming method, the apparatuses, methods, and the like described in paragraphs “0196” to “0229” of Japanese Patent Application Laid-Open No. 2010-2897 can be appropriately employed. .

  Examples of the present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 Preparation of Toner 1
(1) Preparation of resin particle dispersion 1 for core (1-1) First stage polymerization An anionic surface activity is previously provided in a reaction vessel equipped with a stirrer, a temperature sensor, a temperature controller, a cooling pipe, and a nitrogen introducing device. An anionic surfactant solution in which 2.0 parts by mass of the agent “sodium lauryl sulfate” was dissolved in 2900 parts by mass of ion-exchanged water was added, and the internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm in a nitrogen stream. Allowed to warm.

After adding 9.0 parts by mass of a polymerization initiator “potassium persulfate (KPS)” to this anionic surfactant solution and adjusting the internal temperature to 78 ° C.,
Solution (1)
Styrene 540 parts by mass n-butyl acrylate 154 parts by mass Methacrylic acid 77 parts by mass n-octyl mercaptan 17 parts by mass A solution (1) was added dropwise over 3 hours. After completion of the dropping, polymerization (first stage polymerization) was carried out by heating and stirring at 78 ° C. for 1 hour to prepare a dispersion of “resin particles [a1]”.

(1-2) Second stage polymerization: formation of an intermediate layer In a flask equipped with a stirrer,
Solution (2)
Styrene 94 parts by weight n-butyl acrylate 60 parts by weight Methacrylic acid 11 parts by weight n-octyl mercaptan 5 parts by weight Paraffin wax (melting point: 73 ° C.) 51 parts by weight as a release agent was added, A monomer solution [2] was prepared by heating to 85 ° C. and dissolving.

  On the other hand, a surfactant solution in which 2 parts by mass of the anionic surfactant “sodium lauryl sulfate” was dissolved in 1100 parts by mass of ion-exchanged water was heated to 90 ° C. After adding 28 parts by mass of the above-mentioned dispersion of “resin particles [a1]” in terms of solid content of the resin fine particles [a1] to this surfactant solution, a mechanical disperser “CLEAMIX (registered) having a circulation path is added. (Trademark) ”(manufactured by M Technique Co., Ltd.), the monomer solution [2] was mixed and dispersed for 4 hours to prepare a dispersion containing emulsified particles having a dispersed particle diameter of 350 nm. An initiator aqueous solution in which 2.5 parts by mass of potassium persulfate (KPS) is dissolved in 110 parts by mass of ion-exchanged water as a polymerization initiator is added to this dispersion, and this system is heated and stirred at 90 ° C. for 2 hours. By performing polymerization (second stage polymerization), a dispersion of “resin particles [a11]” was prepared.

(1-3) Third-stage polymerization: formation of outer layer In the above dispersion of “resin particles [a11]”, 2.5 parts by mass of potassium persulfate (KPS) as a polymerization initiator is added to 110 parts by mass of ion-exchanged water. Add the dissolved initiator aqueous solution, and under the temperature condition of 80 ° C,
Solution (3)
Styrene 230 mass parts n-butyl acrylate 100 mass parts n-octyl mercaptan Solution (3) which consists of 5.2 mass parts was dripped over 1 hour. After completion of the dropwise addition, polymerization (third stage polymerization) was performed by heating and stirring for 3 hours. Then, it cooled to 28 degreeC and prepared "the resin particle for core [a] dispersion liquid 1".

(2) Preparation of resin particle dispersion 1 for shell (2-1) Synthesis of amorphous polyester resin [a] In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube,
Bisphenol A propylene oxide 2-mole adduct 316 parts by weight Terephthalic acid 80 parts by weight Fumaric acid 34 parts by weight Polycondensation catalyst (titanium tetraisopropoxide) 2 parts by weight divided into 10 portions, at 200 ° C under a nitrogen stream The reaction was carried out for 10 hours while distilling off the generated water.

  Subsequently, it was made to react under reduced pressure of 13.3 kPa (100 mmHg), and it took out when the softening point became 104 degreeC. This was designated as an amorphous polyester resin [a]. The glass transition point of the amorphous polyester resin [a] measured by the DSC method was 52 ° C.

(2-2) Preparation of Resin Particle Particle Dispersion 1 1 As a shell resin, 100 parts by mass of the amorphous polyester resin [a] obtained above was dissolved in 400 parts by mass of ethyl acetate.

  Subsequently, 25 mass parts of 5.0 mass% sodium hydroxide aqueous solution was added, and the resin solution was formed. This resin solution was put into a container having a stirrer, and 638 parts by mass of a 0.26% by mass aqueous sodium lauryl sulfate solution was dropped and mixed over 30 minutes while stirring the resin solution. After the whole amount of the sodium lauryl sulfate aqueous solution was dropped, an emulsion in which the resin solution particles were uniformly dispersed was obtained.

  Next, the emulsion was heated to 40 ° C., and using a diaphragm vacuum pump “V-700” (manufactured by BUCHI), ethyl acetate was distilled off under reduced pressure of 150 hPa to obtain “for shell use”. Dispersion 1 ”was obtained on resin particles [a].

  (3) Preparation of pigment particle dispersion

50 ml of toluene and 0.53 g of morpholine are added with stirring to intermediate 1.93 g synthesized according to the method described in JP-A 2010-100532 and intermediate 2: 1.53 g synthesized according to a conventional method. The mixture was heated to reflux and reacted for 8 hours while dehydrating with an ester tube. After completion of the reaction, the reaction mixture was concentrated, purified by column chromatography, and recrystallized from a mixed solvent of ethyl acetate / hexane to obtain 2.71 g of the compound represented by the above formula (DX-1). It was identified by the MASS spectrum, ¹ H-NMR spectrum, and IR spectrum, and confirmed to be the target product. Visible absorption spectrum measurement (solvent: ethyl acetate) Maximum absorption wavelength: 535 nm, molar extinction coefficient: 71000 (L / mol · cm).

  A surfactant aqueous solution was prepared by stirring and dissolving 11.5 parts by mass of sodium n-dodecyl sulfate in 160 parts by mass of ion-exchanged water. To this surfactant aqueous solution, 20 parts by mass of the compound represented by the above formula (DX-1) as a colorant is gradually added, and then “CLEARMIX (registered trademark) W motion CLM-0.8” (M -The pigment dispersion liquid 1 in which the particle | grains of the pigment | dye (DX-1) were disperse | distributed was prepared by carrying out a dispersion process using Technique Co., Ltd. product.

  The volume-based median diameter of the colorant particles in the pigment dispersion 1 was measured to be 221 nm.

  The volume-based median diameter is “MICROTRAC UPA-150” (manufactured by HONEYWELL), sample refractive index 1.59, sample specific gravity 1.05 (in terms of spherical particles), solvent refractive index 1.33, solvent viscosity. The measurement was performed by adjusting the zero point by introducing ion-exchanged water into the measurement cell under the measurement conditions of 0.797 (30 ° C.) and 1.002 (20 ° C.).

  (4) Synthesis of metal compound 1-55 and preparation of dispersion

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

Synthesis of Compound C 5 g of Compound B, 25 ml of toluene, 3.3 g of triethylamine and 2.42 g of calcium chloride were added to a 100 ml three-necked flask and heated to 80 ° C. and stirred. After the internal temperature reached 80 ° C., 2.1 g of acetyl chloride was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was cooled, separated with dilute hydrochloric acid, neutralized with pure water, and the solvent was distilled off. Thereafter, 50 g of toluene and 50 ml of ethyl acetate were added and recrystallized to obtain 4.3 g of Compound C.

Synthesis of Metal Compound 1-55 2 g of Compound C and 80 ml of acetone were added to a 200 ml three-necked flask and heated and stirred until the internal temperature reached 55 ° C. Thereafter, 0.55 g of copper acetate monohydrate was dissolved in 5 ml of a solvent of MeOH / water = 5/1 (mass ratio) and added dropwise over 30 minutes. After completion of dropping, 1.4 g of metal compound 1-55 was obtained by filtering the precipitated solid.

Preparation of dispersion of metal compound 1-55 30 g of metal compound 1-55 was added to a solution prepared by dissolving 4.9 g of sodium dodecyl sulfate in 120 ml of pure water, and stirred to give a solid content. A dispersion of 20% by mass of metal compound 1-55 was prepared.

(5) Preparation of dispersion of toner base particles 1 (aggregation / fusion process)
In a reaction vessel equipped with a stirrer, a temperature sensor, and a cooling pipe, 288 parts by mass of the “dispersed liquid of core resin particles [A]” prepared in (1) above in terms of solid content and 2000 parts by mass of ion-exchanged water Was added and a 5 mol / liter aqueous sodium hydroxide solution was added to adjust the pH to 10 at 25 ° C.

  Next, an aqueous solution in which 60 parts by mass of magnesium chloride was dissolved in 60 parts by mass of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring.

After standing for 3 minutes, the temperature was raised and the system was heated to 80 ° C. over 60 minutes, and the particle growth reaction was continued while maintaining 80 ° C. In this state, the particle size of the particles was measured with “Coulter Multisizer 3” (manufactured by Beckman Coulter Co., Ltd.), and when the median diameter (D ₅₀ ) on the volume basis became 6.5 μm, “Shell Resin When 72 parts by mass of the dispersion [1] of particles [a] is charged over 30 minutes and the supernatant of the reaction solution becomes transparent, the dispersion of the metal compound 1-55 is used as a binder resin. It was dripped so that it might become 3 mass% with respect to it. When the supernatant of the reaction solution became transparent, an aqueous solution in which 190 parts by mass of sodium chloride was dissolved in 760 parts by mass of ion-exchanged water was added to stop particle growth.

  Further, the temperature is raised and the particles are fused by heating and stirring at 90 ° C., and the average circularity measuring device “FPIA-2100” (manufactured by Sysmex Corporation) is used (HPF). The number of detection was 4000), and when the average circularity reached 0.945, it was cooled to 30 ° C. to prepare “dispersion of toner base particle 1”.

(6) Washing Step The particles produced in the step (5) (“Dispersion of toner base particle 1”) were solid-liquid separated with a centrifuge to form a wet cake of toner base particles. The wet cake was washed with ion-exchanged water at 35 ° C. until the electric conductivity of the filtrate reached 5 μS / cm in the centrifuge.

(7) Drying Step After the above (6) washing step, the wet cake is transferred to “Flash Jet Dryer” (manufactured by Seishin Enterprise Co., Ltd.) and dried until the water content becomes 0.5 mass%. Was made.

(8) Preparation of external additive: Preparation of large-diameter silica A The following were prepared as external additives.

  (8-1) 630 parts by mass of methanol and 90 parts by mass of water were added to and mixed with a 3 liter reactor equipped with a stirrer, a dropping funnel, and a thermometer. While stirring this solution, 800 parts by mass of tetramethoxysilane was hydrolyzed (catalyst: ammonia) to obtain a suspension of silica fine particles. Subsequently, it heated at 60-70 degreeC, 390 mass parts of methanol was distilled off, and the aqueous suspension of the silica fine particle was obtained.

  (8-2) To this aqueous suspension, 11.6 parts by mass of methyltrimethoxysilane (corresponding to 0.1 molar ratio with respect to tetramethoxysilane) was added dropwise at room temperature (25 ° C.) to obtain silica. The surface of the fine particles was treated to obtain a dispersion.

  (8-3) 1400 parts by mass of methyl isobutyl ketone was added to the dispersion thus obtained, and then heated to 80 ° C. to distill off methanol water. To the obtained dispersion, 240 parts by mass of hexamethyldisilazane was added at room temperature (25 ° C.), heated to 120 ° C. and reacted for 3 hours to trimethylsilylate the silica fine particles. Thereafter, the solvent was distilled off under reduced pressure to prepare large-diameter silica A.

For the large size silica A obtained by the above method, according to the method described above, it was measured volume average primary particle size was found to be the volume average primary particle diameter D _{50 =} 80 nm (standard deviation = 12 nm).

(9) External additive treatment step In the above-mentioned “toner base particles (1)”, 1% by mass of the large-diameter silica A obtained above and 1% by mass of hydrophobic silica (number average primary particle size = 12 nm). And 0.3% by mass of hydrophobic titania (number average primary particle size = 20 nm) were added and mixed with a Henschel mixer to prepare “Toner 1”.

(Example 2: Preparation of toner 2)
The “amorphous polyester resin [b]” was prepared by the following procedure, used in place of the “amorphous polyester resin [a]”, and the metal compound 1-55 was used as the metal compound 1-36. “Toner 2” was prepared in the same procedure as in Example 1 except for the change.

  Metal compound 1-55 was synthesized in the same manner as in Example 1 except that acetyl chloride was changed to trifluoroacetic anhydride in the synthesis of compound C of Example 1 above.

Preparation of Amorphous Polyester Resin [b] In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 316 parts by mass of bisphenol A propylene oxide 2 mol adduct, 95 parts by mass of terephthalic acid, 19 parts by mass of fumaric acid As a polycondensation catalyst, 2 parts by mass of titanium tetraisopropoxide was added in 10 portions and reacted at 200 ° C. for 10 hours while distilling off the water produced under a nitrogen stream.

  Subsequently, it was made to react under reduced pressure of 13.3 kPa (100 mmHg), and it pick_out | removed when the softening point became 104 degreeC. This was designated as amorphous polyester resin [b]. The glass transition point of the amorphous polyester resin [b] measured by the DSC method was 64 ° C.

(Example 3: Preparation of toner 3)
“Toner 3” was prepared in the same manner as in Example 2 except that “amorphous polyester resin [c]” was prepared by the following procedure and used in place of “amorphous polyester resin [a]”. Was made.

Preparation of non-crystalline polyester resin [c] In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 316 parts by mass of bisphenol A propylene oxide 2 mol adduct, 65 parts by mass of terephthalic acid, 49 parts by mass of fumaric acid As a polycondensation catalyst, 2 parts by mass of titanium tetraisopropoxide was added in 10 portions and reacted at 200 ° C. for 10 hours while distilling off the water produced under a nitrogen stream.

  Subsequently, it was made to react under reduced pressure of 13.3 kPa (100 mmHg), and it pick_out | removed when the softening point became 104 degreeC. This was designated as an amorphous polyester resin [c]. The glass transition point of the amorphous polyester resin [c] measured by the DSC method was 45 ° C.

(Example 4: Preparation of toner 4)
Toner 4 was produced in the same manner as in Example 1 except that the dye DX-1 was changed to the dye represented by the above chemical formula DX-5.

  DX-5 was synthesized in the same manner as in Example 1 except that the intermediate 2 was changed to the following intermediate 3 in the preparation of (3) the dye particle dispersion in Example 1.

(Example 5: Preparation of toner 5)
“Amorphous polyester resin [d]” was prepared in the following procedure and used in place of “Amorphous polyester resin [a]”; Dye DX-5 was used in place of Dye DX-1 Example 1 except that a compound having the structure shown in Table 1 was used in place of metal compound 1-55 and that large-diameter silica B prepared as follows was used in place of large-diameter silica A. In the same procedure, “Toner 5” was produced.

  In addition, the metal compound was synthesize | combined like Example 1 except having changed the copper acetate monohydrate into the magnesium acetate tetrahydrate in the synthesis | combination of the metal compound 1-55 of Example 1. FIG.

Preparation of large-diameter silica B In preparation of large-diameter silica A, the same procedure as in (8) of Example 1 was conducted, except that tetramethoxysilane was changed to 650 parts by mass and hexamethyldisilazane was changed to 210 parts by mass. Thus, a large-diameter silica B having a volume average particle diameter D ₅₀ = 60 nm (standard deviation = 12 nm) was obtained.

Preparation of Amorphous Polyester Resin [d] In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 316 parts by mass of bisphenol A propylene oxide 2 mol adduct, 100 parts by mass of terephthalic acid, 14 parts by mass of fumaric acid As a polycondensation catalyst, 2 parts by mass of titanium tetraisopropoxide was added in 10 portions and reacted at 200 ° C. for 10 hours while distilling off the water produced under a nitrogen stream.

  Subsequently, it was made to react under reduced pressure of 13.3 kPa (100 mmHg), and it pick_out | removed when the softening point became 104 degreeC. This was designated as amorphous polyester resin [d]. The glass transition point of the amorphous polyester resin [d] measured by DSC method was 67 ° C.

(Example 6: Preparation of toner 6)
“Toner 6” was prepared in the same manner as in Example 5 except that “amorphous polyester resin [e]” was prepared by the following procedure and used in place of “amorphous polyester resin [d]”. Was made.

Preparation of Amorphous Polyester Resin [e] In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube, 316 parts by mass of bisphenol A propylene oxide 2 mol adduct, 60 parts by mass of terephthalic acid, 54 parts by mass of fumaric acid As a polycondensation catalyst, 2 parts by mass of titanium tetraisopropoxide was added in 10 portions and reacted at 200 ° C. for 10 hours while distilling off the water produced under a nitrogen stream.

  Subsequently, it was made to react under reduced pressure of 13.3 kPa (100 mmHg), and it pick_out | removed when the softening point became 104 degreeC. This was designated as amorphous polyester resin [e]. The glass transition point of the amorphous polyester resin [e] measured by the DSC method was 43 ° C.

Example 7 Production of Toner 7
The “shell resin particles [f]” were prepared by the following procedure, used in place of “amorphous polyester resin [a]”, and prepared as follows instead of large-diameter silica A. A toner 7 was produced in the same manner as in Example 4 except that the diameter silica C was used.

Preparation of “dispersion 1 of resin particles for shell [f] 1” Anionic surfactant (sodium dodecylbenzenesulfonate: SDS) 2 was placed in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device. A surfactant solution in which 0.0 part by mass was dissolved in 2900 parts by mass of ion-exchanged water was added, and the internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm in a nitrogen stream.

After adding 9.0 parts by mass of a polymerization initiator (potassium persulfate: KPS) to the surfactant solution and setting the internal temperature to 78 ° C,
Styrene 604 parts by mass n-butyl acrylate 166 parts by mass Methacrylic acid 105 parts by mass n-Octyl mercaptan 9 parts by mass A monomer mixed solution was added dropwise over 3 hours. After completion of the dropwise addition, the polymerization reaction was carried out by heating and stirring at 78 ° C. for 1 hour to prepare a dispersion of resin particles. This resin particle dispersion was designated as “dispersion 1 of shell resin particles [f]”. The glass transition temperature of the resin particles for shell [f] measured by the DSC method was 65 ° C.

Preparation of large-diameter silica C In the preparation of large-diameter silica A, the same procedure as in (8) of Example 1 except that tetramethoxysilane was changed to 1500 parts by mass and hexamethyldisilazane was changed to 360 parts by mass. The large-diameter silica C having a volume average particle diameter D ₅₀ = 150 nm (standard deviation = 26 nm) was obtained.

Example 8 Production of Toner 8
In the production of “dispersion liquid 1 of shell resin particles [f]”, the addition amount of each compound was changed as follows to produce “dispersion liquid 1 of shell resin particles [g]” and a large diameter. Toner 8 was produced in the same manner as in Example 4 except that large-diameter silica D prepared as follows was used instead of silica A.

Styrene 517 parts by mass n-butyl acrylate 254 parts by mass Methacrylic acid 105 parts by mass n-octyl mercaptan 48 parts by mass The glass transition temperature of the resin particles for shell [g] measured by the DSC method was 65 ° C.

Preparation of large-diameter silica D In preparation of large-diameter silica A, the same procedure as in (8) of Example 1 except that tetramethoxysilane was changed to 900 parts by mass and hexamethyldisilazane was changed to 260 parts by mass. The large-diameter silica D having a volume average particle diameter D ₅₀ = 150 nm (standard deviation = 26 nm) was obtained.

Example 9 Production of Toner 9
Toner 9 was produced in the same manner as in Example 2 except that the large diameter silica B was used instead of the large diameter silica A.

Example 10 Production of Toner 10
In the production of “Toner 1”, “dispersion of core resin particles [A]” was used in an amount of 360 parts by mass in terms of solid content. After the particle growth reaction, when the volume-based median diameter (D ₅₀ ) reached 6.2 μm, the “dispersion liquid 1 of the shell resin particles [a]” was not added, but the dispersion liquid of the metal compound 1-36 The toner 10 was prepared in the same procedure as in Example 1 except that the large-diameter silica C was used instead of the large-diameter silica A.

(Comparative Example 1: Preparation of Toner 11)
Toner 11 was prepared in the same procedure as in Example 1 except that large-diameter silica A was not used.

(Comparative Example 2: Preparation of Toner 12)
Toner 12 was prepared in the same procedure as in Example 1 except that large-diameter silica E prepared as described below was used instead of large-diameter silica A.

Preparation of large-diameter silica E In preparation of large-diameter silica A, the same procedure as in (8) of Example 1 except that tetramethoxysilane was changed to 1650 parts by mass and hexamethyldisilazane was changed to 390 parts by mass. A large-diameter silica E having a volume average particle diameter D ₅₀ = 180 nm (standard deviation = 27 nm) was obtained.

(Comparative Example 3: Preparation of Toner 13)
Toner 13 was produced in the same procedure as in Example 2 except that large-diameter silica F prepared as follows was used instead of large-diameter silica A.

Preparation of large-diameter silica F Preparation of large-diameter silica A was carried out in the same manner as in Example 1 (8) except that tetramethoxysilane was changed to 600 parts by mass and hexamethyldisilazane was changed to 200 parts by mass. The large-diameter silica F having a volume average particle diameter D ₅₀ = 55 nm (standard deviation = 11 nm) was obtained.

(Comparative Example 4: Preparation of Toner 14)
Toner 14 was produced in the same procedure as in Example 2 except that large-diameter silica G prepared as follows was used instead of large-diameter silica A.

Preparation of large-diameter silica G In the preparation of large-diameter silica A, the same procedure as in Example 1 (8) was conducted except that tetramethoxysilane was changed to 1600 parts by mass and hexamethyldisilazane was changed to 380 parts by mass. A large-diameter silica G having a volume average particle diameter D ₅₀ = 155 nm (standard deviation = 27 nm) was obtained.

(Comparative Example 5: Preparation of toner 15)
As a colorant, C.I. I. Toner 15 was prepared in the same procedure as in Example 1 except that Pigment Red 122 (quinacridone pigment, see the chemical formula below) was used.

  The configurations of the toners of the examples and comparative examples obtained above are shown in Table 1 below.

≪Evaluation≫
(Image evaluation)
Using a commercially available digital color multifunction device “bizhub (registered trademark) PRO C6500” (manufactured by Konica Minolta Business Technologies, Inc.) as an evaluation device, the toner manufactured above and a developer are sequentially loaded and image evaluation is performed. It was.

(Density difference)
The image density is an initial image density in a low-temperature and low-humidity environment (10 ° C., 20% RH), and an image density obtained by printing a 10 cm square solid image after printing 10,000 sheets of character images with a printing rate of 5%. Ten points were randomly measured with a reflection densitometer “RD-918 (manufactured by Macbeth), and the average density was evaluated.

(saturation)
“Saturation” is a value indicating the degree of vividness of a color, and specifically, L * a * b * color system [CIE (International Lighting Commission) 1976 (L * a * b *). The value obtained from the value of a * and b * measured based on the color space] according to the following equation (1).

Formula (1): Saturation C * = [(a *) ² + (b *) ² ] ^1/2
Here, the L * a * b * color system is a means that is useful for expressing a color numerically, L * is a coordinate in the z-axis direction and represents lightness, and a * and b * Is the coordinate on the x-axis and y-axis, respectively, a * indicates the hue in the red-green direction, b * indicates the hue in the yellow-blue direction, and both represent saturation.

  Saturation C * is specifically represented by the distance from the origin O of the coordinate point (a, b).

  Lightness refers to the relative brightness of colors that can be compared regardless of hue, and hue refers to shades of red, yellow, green, blue, purple, and the like.

  The L * a * b * color system for calculating the saturation C * is specifically a spectrophotometer “Gretag Macbeth Spectrolino” (manufactured by Gretag Macbeth), a D65 light source, and a reflection measurement. The aperture is φ4 mm, the measurement wavelength range is 380 to 730 nm at intervals of 10 nm, the viewing angle (observer) is 2 °, and the reference alignment is measured under the condition using a dedicated white tile.

(Fog density)
First, with respect to A4 size white paper before image formation, the density of the white paper was calculated by measuring and averaging 20 absolute image densities using a reflection densitometer “RD-918 (manufactured by Macbeth)”.

  In a normal temperature and humidity environment with a temperature of 20 ° C. and a relative humidity of 50% RH, 500,000 character images with a printing rate of 5% were printed on A4 size fine paper, and then a blank paper was printed. For the white paper, the average image density was calculated by measuring and averaging the absolute image density at 20 locations in the same manner as described above, and the value obtained by subtracting the white paper density from this average density was evaluated as the fog density.

  The evaluation results are shown in Table 2 below.

  As is apparent from Table 2 above, it was found that the toners of Examples 1 to 10, which are toners for developing electrostatic images according to the present invention, can stably output high saturation and high density images during continuous printing. .

Claims (4)

At least with a binder resin,
A colorant comprising a dye represented by the following general formula (1) and a metal compound represented by the following chemical formula (2);
An external additive containing silica fine particles having a volume average primary particle diameter of 60 to 150 nm formed by a sol-gel method;
Toner for developing electrostatic image containing:
In the general formula (1),
Rx ₁ and Rx ₂ are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Lx is a hydrogen atom or a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Gx ₁ is a linear, branched, or cyclic alkyl group or unsubstituted C2-20 substituted,
Gx ₂ is a substituted or unsubstituted linear or branched alkyl group having 1 to 5 carbon atoms,
Gx ₃ is a hydrogen atom, a halogen atom, a group represented by Gx ₄ —CO—NH—, or a group represented by Gx ₅ —N (Gx ₆ ) —CO—, wherein Gx ₄ is a substituent. Gx ₅ and Gx ₆ are each independently a hydrogen atom or a substituent,
Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently a hydrogen atom or a substituent,
In the general formula (2),
M is a divalent metal,
R ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
R ₂ is a hydrogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a halogen atom, or a cyano group,
R ₃ is a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms.   The electrostatic image developing toner according to claim 1, which has a core-shell structure including a core part and a shell part.   The electrostatic charge image developing toner according to claim 2, wherein the resin constituting the shell portion is a polyester resin.   The electrostatic charge image developing toner according to claim 2 or 3, wherein a glass transition temperature of a resin constituting the shell portion is 45 to 65 ° C.