Toner for developing electrostatic latent image

文档序号：1830558 发布日期：2021-11-12 浏览：12次中文

阅读说明：本技术 静电潜像显影用调色剂 (Toner for developing electrostatic latent image ) 是由樱田育子宫岛谦史萱森隆成于 2021-04-22 设计创作，主要内容包括：本发明的问题在于：提供一种抑制环境变动中的带电量的变动和画质降低,具有优异的颜色再现性和低温定影性的静电潜像显影用调色剂。本发明的静电潜像显影用调色剂,其为包含至少含有调色剂母体粒子和外部添加剂的调色剂粒子的静电潜像显影用调色剂,所述调色剂母体粒子含有着色剂和粘结树脂,所述着色剂含有具有下述通式(1)表示的结构的化合物配位至下述通式(2)表示的结构表示的含金属化合物而得到的着色剂,所述外部添加剂是一次粒子的数均粒径为8～50nm的范围内并且进行了疏水性表面修饰的氧化铝微粒,并且,相对于所述调色剂母体粒子100质量份,所述调色剂在0.1～2.0质量份的范围内包含所述外部添加剂。[化学式1][化学式2]通式(2)(The problems of the invention are that: provided is a toner for developing an electrostatic latent image, which suppresses the fluctuation of the charge amount and the degradation of the image quality in environmental changes and has excellent color reproducibility and low-temperature fixability. The toner for electrostatic latent image development of the present invention is a toner for electrostatic latent image development comprising toner particles containing at least toner base particles containing a colorant and a binder resin, the colorant containing a colorant obtained by coordinating a compound having a structure represented by the following general formula (1) to a metal-containing compound having a structure represented by the following general formula (2), and an external additive being alumina fine particles having a number average particle diameter of primary particles in the range of 8 to 50nm and having a hydrophobic surface modification, wherein the external additive is 100 parts by mass of the toner base particles,the toner contains the external additive in the range of 0.1 to 2.0 parts by mass. [ chemical formula 1] [ chemical formula 2]General formula (2))

1. A toner for electrostatic latent image development, which is a toner for electrostatic latent image development comprising toner particles containing at least toner base particles and an external additive, wherein,

the toner base particles contain a colorant and a binder resin,

the colorant contains: a colorant obtained by coordinating a compound having a structure represented by the following general formula (1) to a metal-containing compound having a structure represented by the following general formula (2),

the external additive is alumina fine particles having a primary particle number average particle diameter of 8 to 50nm and subjected to hydrophobic surface modification,

the toner contains the external additive in a range of 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the toner parent particles,

[ chemical formula 1]

General formula (1)

In the formula (1), the reaction mixture is,

Rx₁and Rx₂Each independently represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,

lx represents a hydrogen atom or a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, Gx1 represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 2 to 20 carbon atoms,

Gx₂represents a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 5 carbon atoms,

Gx₃represents a hydrogen atom, a halogen atom, Gx₄A group represented by-CO-NH-or Gx₅-N(Gx₆) A group represented by-CO-, Gx₄Represents a substituent group, Gx₅And Gx₆Each independently represents a hydrogen atom or a substituent,

Qx₁、Qx₂、Qx₃、Qx₄and Qx₅Each independently represents a hydrogen atom or a substituent,

[ chemical formula 2]

General formula (2)

In the formula (2), the reaction mixture is,

R₁represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

R₂Represents a hydrogen atom, an alkoxycarbonyl group, an arylcarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a nitrophenyl group, a halogen atom or a cyano group,

R₃represents a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms.

M represents a 2-valent metal element.

2. The toner for electrostatic latent image development according to claim 1, wherein,

the amount of carbon remaining on the surface of the surface-modified alumina fine particles is in the range of 0.5 to 10 mass% relative to the alumina fine particles.

3. The toner for electrostatic latent image development according to claim 1 or 2, wherein,

the alumina fine particles having a hydrophobic surface modification are alumina fine particles having a hydrophobic surface modification by a silane coupling agent represented by the following formula (1),

formula (1): x_n-Si(OR)_m

In the formula (1), X represents an alkyl group having 1-16 carbon atoms, R represents a methyl group or an ethyl group, n represents 1 or 2, m represents 2 or 3, and n + m represents 4.

4. The toner for developing an electrostatic latent image according to any one of claims 1 to 3,

the glass transition temperature is in the range of 30-65 ℃.

5. The toner for developing an electrostatic latent image according to any one of claims 1 to 4,

the toner matrix particles contain an amorphous polyester resin as a binder resin.

[ technical field ]

The present invention relates to a toner for developing an electrostatic latent image. More specifically, the present invention relates to: a toner for developing electrostatic latent images, which suppresses image quality degradation due to environmental changes and has excellent color reproducibility and low-temperature fixability.

[ background art ]

In recent years, there has been an increasing demand for high-definition and high-quality images, and a high color reproducibility has been required for an electrostatic latent image developing toner (hereinafter, also simply referred to as "toner") for forming images. In general, an organic pigment or an oil-soluble dye is required to function for color reproducibility, but these are difficult to obtain good dispersibility and thus have low transparency, and thus sufficient color reproducibility cannot be obtained.

As a countermeasure for this, patent document 1 proposes: a method of obtaining sufficient color reproducibility by improving dispersibility in a toner by using a colorant containing a colorant precursor and a metal-containing compound.

On the other hand, in recent years, from the viewpoint of energy saving, development of low-temperature fixing toner has been made so that a resin of the toner has a property of being easily moved by heat. Therefore, when the colorant is used in such a low-temperature fixing toner, it is found that the deterioration of the image quality becomes remarkable particularly under high temperature and high humidity.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open publication No. 2009-282351

[ summary of the invention ]

[ problem to be solved by the invention ]

The present invention has been made in view of the above problems and circumstances, and an object of the present invention is to provide a toner for developing an electrostatic latent image, which suppresses image quality degradation due to environmental changes and has excellent color reproducibility and low-temperature fixability.

[ means for solving problems ]

The present inventors have studied the cause of the above-mentioned problems in order to solve the above-mentioned problems, and as a result, have found that: the present inventors have completed the present invention by realizing a toner which can suppress the deterioration of image quality particularly under high temperature and high humidity conditions by using toner base particles containing a colorant having a metal element and alumina fine particles having a hydrophobic surface modification as an external additive.

That is, the above-described problem of the present invention is solved by the following means.

the toner base particles contain a colorant and a binder resin,

the external additive is alumina fine particles having a primary particle number average particle diameter of 8 to 50nm and subjected to hydrophobic surface modification,

the toner contains the external additive in a range of 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the toner parent particles,

[ chemical formula 1]

(in the formula, wherein,

Rx₁and Rx₂Each independently represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

Lx represents a hydrogen atom or a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Gx1 represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 2 to 20 carbon atoms.

Gx₂Represents a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 5 carbon atoms.

Gx₃Represents a hydrogen atom, a halogen atom, Gx₄A group represented by-CO-NH-or Gx₅-N(Gx₆) A group represented by-CO-, Gx₄Represents a substituent group, Gx₅And Gx₆Each independently represents a hydrogen atom or a substituent.

Qx₁、Qx₂、Qx₃、Qx₄And Qx₅Each independently represents a hydrogen atom or a substituent. )

[ chemical formula 2]

(in the formula, wherein,

R₁represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

R₃Represents a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms.

M represents a 2-valent metal element. )

2. The toner for developing an electrostatic latent image according to claim 1, wherein,

the amount of carbon remaining on the surface of the surface-modified alumina fine particles is in the range of 0.5 to 10 mass% relative to the alumina fine particles.

3. The toner for developing an electrostatic latent image according to claim 1 or 2, wherein,

Formula (1): x_n-Si(OR)_m

(wherein X represents an alkyl group having 1 to 16 carbon atoms, R represents a methyl group or an ethyl group, n represents 1 or 2, m represents 2 or 3, and n + m represents 4.)

4. The toner for developing an electrostatic latent image according to any one of items 1 to 3, wherein,

the glass transition temperature is in the range of 30-65 ℃.

5. The toner for developing an electrostatic latent image according to any one of items 1 to 4, wherein,

the toner matrix particles contain an amorphous polyester resin as a binder resin.

[ Effect of the invention ]

By the means of the present invention, it is possible to provide: a toner for developing electrostatic latent images, which suppresses image quality degradation due to environmental changes and has excellent color reproducibility and low-temperature fixability. The mechanism of expression or action of the effect of the present invention is not clearly understood, but the following is presumed.

In the case where a colorant is contained in the low-temperature fixing toner, the mechanism of occurrence of image degradation is considered as follows. It is clear that the colorant contained in the low-temperature fixing toner is low-molecular and therefore slowly moves to the toner surface during toner production due to the polarity of the metal ion that the colorant has. And (3) presuming: the colorant having a metal ion is present in the vicinity of the toner surface, and is easily coordinated with water molecules in the air, and particularly, deterioration of an image becomes remarkable with low charging of the toner under high humidity and high temperature.

It is known that the ease of coordination of water molecules on the surface of toner base particles can be suppressed by adding external additive particles having surfaces subjected to hydrophobic treatment. In general, the external additives include: the fine powder of the inorganic oxide is usually silica, titania, and alumina. The surface of the external additive needs to be subjected to a hydrophobization treatment to an extent that can suppress coordination of water molecules, and as the amount of the hydrophobization treatment agent increases, the resistance of particles increases, and image quality is lowered due to transfer failure, and therefore, it is necessary to reduce the resistance of the matrix itself of the inorganic fine particles as low as possible.

In addition, in the present study, it is found that the larger the refractive index of the inorganic fine particles is, the more the reflected light is dispersed, and the color reproducibility is lowered, and therefore, it is necessary to make the refractive index of the inorganic fine particles itself as small as possible.

As a result of intensive studies, it was found that: when the both conditions are satisfied, the effect is remarkable in the case of alumina fine particles, particularly particles having a number average particle diameter of primary particles in the range of 8 to 50 nm. It is found that: in the case of less than 8nm, the effect is reduced by burying the surface of the toner matrix, and in the case of more than 50nm, the influence of the refractive index is large, so that the color reproducibility is reduced. Furthermore, it was found that: the content of the alumina fine particles is in the range of 0.1 to 2.0 parts by mass relative to 100 parts by mass of the toner base particles, so that the effects of inhibiting coordination of water molecules and ensuring color reproducibility can be obtained.

[ detailed description of the invention ]

The toner for electrostatic latent image development comprises toner particles containing at least toner base particles and an external additive, wherein the toner base particles contain a colorant and a binder resin, the colorant contains a colorant obtained by coordinating a compound having a structure represented by the general formula (1) to a metal-containing compound represented by the general formula (2), the external additive is alumina fine particles having a primary particle number average particle diameter of 8-50 nm and subjected to hydrophobic surface modification, and the toner contains the external additive in a range of 0.1-2.0 parts by mass relative to 100 parts by mass of the toner base particles. This feature is a feature common to or corresponding to each embodiment (mode) described below.

In an embodiment of the present invention, the content of carbon remaining on the surface of the surface-modified alumina fine particles is preferably in the range of 0.5 to 10 mass% relative to the alumina fine particles from the viewpoints of suppressing coordination of water molecules and suppressing excessive charging.

In the present invention, the alumina fine particles subjected to hydrophobic surface modification are preferably alumina fine particles subjected to hydrophobic surface modification by the silane coupling agent represented by the formula (1). This can provide an effect of suppressing the coordination of water molecules.

A glass transition temperature in the range of 30 to 65 ℃ is preferable from the viewpoint that the external additive is not easily buried, variation in the amount of charge under high temperature and high humidity is suppressed, and low temperature fixability is ensured.

In an embodiment of the present invention, the toner matrix particles preferably contain an amorphous polyester resin as a binder resin. This can provide excellent color reproducibility.

The present invention and its constituent elements, and specific embodiments and modes of the present invention will be described in detail below. In the present application, "to" is used in the sense of including numerical values described before and after the "to" as the lower limit value and the upper limit value.

In the present invention, the toner is an aggregate of toner particles, and the toner particles are composed of toner base particles and external additives attached to the surfaces thereof.

Further, the toner may be a one-component developer or a two-component developer. The single-component developer is composed only of toner particles, and the two-component developer is composed of toner particles and carrier particles.

Electrostatic latent image developing toner

The toner for electrostatic latent image development of the present invention is a toner for electrostatic latent image development comprising toner particles containing at least toner base particles and an external additive, the toner being characterized in that,

the toner base particles contain a colorant and a binder resin,

the colorant contains a colorant obtained by coordinating a compound having a structure represented by general formula (1) to a metal-containing compound having a structure represented by general formula (2),

the external additive is alumina fine particles having a primary particle number average particle diameter of 8 to 50nm and subjected to hydrophobic surface modification,

the toner contains the external additive in a range of 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the toner parent particles.

[ chemical formula 3]

(in the formula, wherein,

Rx₁and Rx₂Each independently represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

Gx₂Represents a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 5 carbon atoms.

Qx₁、Qx₂、Qx₃、Qx₄And Qx₅Each independently represents a hydrogen atom or a substituent. )

[ chemical formula 4]

(in the formula, wherein,

R₁represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

R₃Represents a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms.

M represents a 2-valent metal element. )

[ toner mother particles ]

The toner base particles of the present invention contain a colorant and a binder resin, and the colorant contains a colorant obtained by coordinating a compound having a structure represented by the general formula (1) to a metal-containing compound having a structure represented by the general formula (2). Further, additives such as a release agent and a charge control agent may be contained as necessary.

< Binder resin >

As the binder resin constituting the toner particles, a known amorphous resin can be used. Specific examples thereof include: vinyl resins, polyurethane resins, urea resins, polyester resins, and the like. In particular, polyester resins are preferred because they have higher polarity than others, are easy to disperse the colorant compound of the present invention, and can provide sufficient color reproducibility.

< polyester resin >

Polyester resins are produced by a polycondensation reaction using a polycarboxylic acid monomer (derivative) and a polyol monomer (derivative) as raw materials in the presence of an appropriate catalyst.

As the polycarboxylic acid monomer derivative, there can be used: alkyl esters, acid anhydrides and acid chlorides of the polycarboxylic acid monomers, as the derivatives of the polyol monomers, ester compounds of the polyol monomers and hydroxycarboxylic acids can be used. Examples of the polycarboxylic acid monomer include: oxalic acid, succinic acid, maleic acid, adipic acid, beta-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3, 5-diene-1, 2-dicarboxylic acid, malic acid, citric acid, hexahydroterephthalic acid, malonic acid, pimelic acid, tartaric acid, mucic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrobenzoic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycolic acid, diphenylacetic acid, diphenyl-p, p '-dicarboxylic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-1, 5-dicarboxylic acid, naphthalene-p' -dicarboxylic acid, naphthalene-1, 5-dicarboxylic acid, sebacic acid, maleic acid, fumaric acid, tartaric acid, muconic acid, phthalic acid, isophthalic acid, maleic acid, isophthalic acid, terephthalic acid, maleic acid, 2-valent carboxylic acids such as naphthalene-2, 6-dicarboxylic acid, anthracenedicarboxylic acid, and dodecenylsuccinic acid; and carboxylic acids having a valence of 3 or more such as trimellitic acid, pyromellitic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, pyrene tricarboxylic acid and pyrene tetracarboxylic acid. As the polycarboxylic acid monomer, an unsaturated aliphatic dicarboxylic acid such as fumaric acid, maleic acid, mesaconic acid, etc. is preferably used, and in particular, an unsaturated aliphatic dicarboxylic acid represented by the above general formula (a) is preferably used. In the present invention, an acid anhydride of a dicarboxylic acid such as maleic anhydride may be used.

Examples of the polyol monomer include: 2-valent alcohols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, hexylene glycol, cyclohexanediol, octanediol, decanediol, dodecanediol, ethylene oxide addition products of bisphenol a, and propylene oxide addition products of bisphenol a; and polyols having a valence of 3 or more, such as glycerol, pentaerythritol, hexamethylolmelamine, hexahydroxyethylmelamine, tetramethylolbenzoguanamine, and tetrahydroxyethylbenzoguanamine.

The polyester resin preferably has a weight average molecular weight (Mw) of 10000 to 100000. The method for producing the polyester resin is not particularly limited, and examples thereof include: a method of polymerizing the above-mentioned monomers by a known polymerization method such as bulk polymerization, solution polymerization, emulsion polymerization, miniemulsion polymerization, dispersion polymerization and the like using any polymerization initiator such as a peroxide, a persulfate, an azo compound and the like which is generally used for polymerization of the above-mentioned monomers. Further, a chain transfer agent generally used may be used for the purpose of adjusting the molecular weight. The chain transfer agent is not particularly limited, and examples thereof include alkyl mercaptans such as n-octyl mercaptan, and mercapto fatty acid esters.

< non-crystalline polyester resin >

The amorphous polyester resin of the present invention generally has no melting point but has a relatively high glass transition temperature (Tg). More specifically, the glass transition temperature (Tg) is preferably in the range of 30 to 65 ℃. When the temperature is 30 ℃ or higher, the external additive is less likely to bury the film, and the coordination of water molecules and the fluctuation of the charge amount under high temperature and high humidity can be suppressed. When the temperature is 65 ℃ or lower, sufficient low-temperature fixability can be maintained.

The non-crystalline polyester resin is contained in an amount of preferably 5 to 95% by mass, more preferably 65 to 95% by mass, even more preferably 70 to 90% by mass, and particularly preferably 80 to 90% by mass, based on the resin component forming the binder resin. By using the amorphous polyester resin in the content within the range, good low-temperature fixability can be obtained.

< crystalline polyester resin >

In addition, regardless of the amorphous resin, a crystalline resin is preferably used in combination from the viewpoint of low-temperature fixability. In particular, from the viewpoint of compatibility with the amorphous resin and manufacturability, a crystalline polyester resin is preferably used. The crystalline polyester resin means: among known polyester resins obtained by the polycondensation reaction of a carboxylic acid (polycarboxylic acid) having a valence of 2 or more and an alcohol (polyol) having a valence of 2 or more, a resin having a sharp endothermic peak (shape in which an endothermic spectrum curve passes through an inflection point to reach the highest point and then falls to the inflection point) without having a stepwise endothermic change in Differential Scanning Calorimetry (DSC).

< styrene-acrylic resin >

As the amorphous resin, a styrene-acrylic resin can be used as needed. The styrene-acrylic resin is a resin having an ethylenically unsaturated bond in which an aromatic vinyl monomer and a (meth) acrylic acid ester monomer are radically polymerizable.

Examples of the aromatic vinyl monomer include: styrene, o-methylstyrene, m-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene, p-n-butylstyrene, p-t-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, 2, 4-dimethylstyrene, 3, 4-dichlorostyrene, and the like, and derivatives thereof.

These aromatic vinyl monomers may be used alone in 1 kind or in combination of 2 or more kinds.

Examples of the (meth) acrylate monomer include: methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, beta-hydroxyethyl acrylate, gamma-aminopropyl methacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

These (meth) acrylate monomers may be used alone in 1 kind or in combination of 2 or more kinds.

< method for measuring glass transition temperature >

The glass transition temperature (Tg) can be measured by differential scanning calorimetry, as described above.

The differential scanning calorimetry of the toner was measured under measurement conditions (temperature rise and cooling conditions) in the order of a1 st temperature rise process in which the temperature was raised from 0 ℃ to 100 ℃ at a rising and falling speed of 10 ℃/min and held at 100 ℃ for 1 minute, a cooling process in which the temperature was cooled from 100 ℃ to 0 ℃ at a cooling speed of 10 ℃/min and held at 0 ℃ for 1 minute, and a2 nd temperature rise process in which the temperature was raised from 0 ℃ to 100 ℃ at a rising and falling speed of 10 ℃/min, using a "diamond DSC" (manufactured by PERKIN ELMER corporation). As a measurement procedure, 5.0mg of toner was enclosed in an aluminum pan and set in a sample holder of "diamond DSC". The control group used an empty aluminum pan.

In the DSC curve described above obtained at the 1 st temperature rise by the differential scanning calorimeter, a base line a immediately before the occurrence of an endothermic peak resulting from enthalpy relaxation and a base line B immediately after the occurrence of an endothermic peak are horizontally plotted, respectively. The intersection C of the line between the midpoints of the base lines a and B and the DSC curve is defined as the glass transition temperature Tg of the toner.

< coloring agent >

The colorant of the present invention is a colorant obtained by coordinating a compound having a structure represented by the following general formula (1) to a metal-containing compound having a structure represented by the following general formula (2).

The compound having the structure represented by the general formula (1) is a pigment, and is preferably coordinated to a metal-containing compound to be used as a colorant.

Hereinafter, a compound having a structure represented by general formula (1) and a metal-containing compound represented by general formula (2) will be described.

(Compound having a structure represented by the general formula (1))

[ chemical formula 5]

(in the formula, wherein,

Rx₁and Rx₂Each independently represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

Lx represents a hydrogen atom or a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

Gx1 represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 2 to 20 carbon atoms.

Gx₂Represents a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 5 carbon atoms.

Qx₁、Qx₂、Qx₃、Qx₄And Qx₅Each independently represents a hydrogen atom or a substituent. )

In the general formula (1), Rx₁And Rx₂Each independently represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Specifically, there may be mentioned: methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, 3-methylpentane-2-yl, 3-methylpentane-3-yl, 4-methylpentyl, 4-methylpentane-2-yl, 1, 3-dimethylbutyl, 3-dimethylbutane-2-yl, n-heptyl, 1-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 1- (n-propyl) butyl, 1-dimethylpentyl, 1, 4-dimethylpentyl, 1-diethylpropyl, diethyl-pentyl, methyl, pentyl, hexyl, pentyl, hexyl, pentyl, hexyl, pentyl, hexyl, pentyl, hexyl, pentyl, hexyl, pentyl, hexyl, pentyl, hexyl, pentyl, hexyl, pentyl, and the amino, hexyl, pentyl, hexyl, pentyl, and the amino, 1,3, 3-trimethylbutyl, 1-ethyl2, 2-dimethylpropyl radical, n-octyl radical, 2-ethylhexyl radical, 2-methylhexan-2-yl radical, 2, 4-dimethylpentan-3-yl radical, 1-dimethylpentan-1-yl radical, 2-dimethylhexan-3-yl radical, 2, 3-dimethylhexan-2-yl radical, 2, 5-dimethylhexan-3-yl radical, 3, 4-dimethylhexan-3-yl radical, 3, 5-dimethylhexan-3-yl radical, 1-methylheptyl radical, 2-methylheptyl radical, 5-methylheptyl radical, 2-methylheptyl radical, 3-methylheptyl radical-2-yl radical, 3-methylheptyl radical-3-yl radical, 4-methylheptan-3-yl, 4-methylheptan-4-yl, 1-ethylhexyl, 2-ethylhexyl, 1-propylpentyl, 2-propylpentyl, 1-dimethylhexyl, 1, 4-dimethylhexyl, 1, 5-dimethylhexyl, 1-ethyl-1-methylpentyl, 1-ethyl-4-methylpentyl, 1, 4-trimethylpentyl, 2,4, 4-trimethylpentyl, 1-isopropyl-1, 2-dimethylpropyl, 1,3, 3-tetramethylbutyl, n-nonyl, 1-methyloctyl, 6-methyloctyl, 1-ethylheptyl, 1- (n-butyl) pentyl, 4-methyl-1- (n-propyl) pentyl, 1-ethylhexyl, 1-ethyl-4-ethylhexyl, 1-ethyl-1-methylpentyl, 1-ethyl-4-methylpentyl, 1, 4-methyl-1- (n-propyl) pentyl, 1-ethyl-4-methylpentyl, 1-ethylpentyl, 4-ethylpentyl, 1-ethylpentyl, 4-ethylpentyl, or a, 1,5, 5-trimethylhexyl, 1, 5-trimethylhexyl, 2-methyloctan-3-yl, n-decyl, 1-methylnonyl, 1-ethyloctyl, 1- (n-butyl) hexyl, 1-dimethyloctyl, 3, 7-dimethyloctyl, n-undecyl, 1-methyldecyl, 1-ethylnonyl, n-dodecyl, 1-methylundecyl, n-tridecyl, n-tetradecyl, 1-methyltridecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-tert-butyl-cyclohexyl and the like.

One or more hydrogen atoms of the alkyl group may be substituted with a substituent. Examples of such substituents include: alkenyl groups (e.g., vinyl, allyl, etc.), alkynyl groups (e.g., ethynyl, propargyl, etc.), aromatic hydrocarbon groups (e.g., phenyl, naphthyl, etc.), aromatic heterocyclic groups (e.g., furyl, thienyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazolyl, triazinyl, imidazolyl, pyrazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, quinazolinyl, phthalazinyl, etc.), heterocyclic groups (e.g., pyrrolidinyl, imidazolidinyl, morpholinyl, oxazolidinyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, propoxy, pentoxy, hexyloxy, octyloxy, dodecyloxy, etc.), cycloalkoxy groups (e.g., cyclopentyloxy, cyclohexyloxy, etc.), aryloxy groups (e.g., phenoxy, naphthyloxy, etc.), alkylthio groups (e.g., methylthio, ethylthio, propylthio, pentylthio, hexylthio, octylthio, dodecylthio, etc.), etc.), Cycloalkylthio (e.g., cyclopentylthio, cyclohexylthio, etc.), arylthio (e.g., phenylthio, naphthylthio, etc.), alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl, etc.), alkoxyalkylenylether (e.g., methoxyethylether), alkylaminocarbonyl (e.g., diethylaminocarbonyl), aryloxycarbonyl (e.g., phenoxycarbonyl, naphthyloxycarbonyl, etc.), phosphoryl (e.g., dimethoxyphosphoryl, diphenylphosphoryl), sulfamoyl (e.g., aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, dodecylaminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl, 2-pyridylaminosulfonyl, etc.), acyl (e.g., acetyl, ethylcarbonyl, propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, etc.), acyloxy (e.g., acetoxy, ethylcarbonyloxy, butylcarbonyloxy, octylcarbonyloxy, dodecylcarbonyloxy, phenylcarbonyloxy, etc.), amide (e.g., methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octylcarbonylamino, dodecylcarbonylamino, phenylcarbonylamino, naphthylcarbonylamino, etc.), carbamoyl (e.g., aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, dodecylcarbonylamino, phenylcarbonylamino, etc.), carbamoyl (e.g., aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, dodecylcarbonylamino, phenylcarbonylamino, etc.), Octylaminocarbonyl, 2-ethylhexylaminocarbonyl, dodecylaminocarbonyl, phenylaminocarbonyl, naphthylaminocarbonyl, 2-pyridylaminocarbonyl and the like), a ureido group (e.g., methylureido, ethylureido, pentylureido, cyclohexylureido, octylureido, dodecylureido, phenylureido, naphthylureido, 2-pyridylaminoureido and the like), a sulfinyl group (e.g., methylsulfinyl, ethylsulfinyl, butylsulfinyl, cyclohexylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, phenylsulfinyl, naphthylsulfinyl, 2-pyridylsulfinyl and the like), an alkylsulfonyl group (e.g., methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl and the like), Arylsulfonyl (phenylsulfonyl, naphthylsulfonyl, 2-pyridylsulfonyl, etc.), amino (e.g., amino, ethylamino, dimethylamino, butylamino, dibutylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, naphthylamino, 2-pyridylamino, etc.), azo (e.g., phenylazo), alkylsulfonyloxy (e.g., methanesulfonyloxy), cyano, nitro, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), hydroxyl, etc., which may further have a substituent. Among these substituents, preferred are: an aromatic hydrocarbon group (preferably having 6 to 20 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms), a cycloalkoxy group (preferably having 4 to 10 carbon atoms), a halogen atom, a hydroxyl group, an alkoxyalkylether group (preferably an alkoxy group having 1 to 10 carbon atoms and an alkylene group having 1 to 10 carbon atoms), or an alkylaminocarbonyl group (preferably an alkyl group having 1 to 10 carbon atoms).

Preferably Rx₁And Rx₂Each independently represents an unsubstituted alkyl group or an alkyl group substituted with an alkoxy group, and more preferably an unsubstituted alkyl group.

Further, Rx₁Number of carbon atoms contained in the alkyl group and Rx used in (1)₂The total number of carbon atoms contained in the alkyl group used in (1) is preferably 2 or more.

In the general formula (1), Lx represents a hydrogen atom or a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Specific examples of alkyl groups and said Rx₁、Rx₂The alkyl group used in (1) is the same, and therefore, a detailed description thereof is omitted here. In addition, specific examples of the substituents and Rx₁、Rx₂The substituents which can be used in (1) are the same, and thus detailed description thereof is omitted here. LX is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atomsMore preferably, a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom.

In the general formula (1), Gx1 represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 2 to 20 carbon atoms. Specific examples of alkyl radicals and said Rx₁、Rx₂The alkyl group used in (1) is the same except for the methyl group, and therefore, the detailed description thereof is omitted here. In addition, specific examples of the substituents and Rx₁、Rx₂The substituents which can be used in (1) are the same, and thus detailed description thereof is omitted here. Gx₁A branched alkyl group is preferred, a 3-stage alkyl group is more preferred, an isopropyl group or a tert-butyl group is still more preferred, and a tert-butyl group is particularly preferred.

In the general formula (1), Gx₂Represents a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 5 carbon atoms. As Gx₂Specific examples of the alkyl group used in (1) include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or neopentyl. Specific examples of the substituents and Rx₁、Rx₂The substituents which can be used in (1) are the same, and thus detailed description thereof is omitted here. From the viewpoint of more effectively obtaining the effects of the present invention, Gx₂Preferably methyl or ethyl.

In the general formula (1), Gx₃Is a hydrogen atom, a halogen atom, Gx₄A group represented by-CO-NH-or Gx₅-N(Gx₆) A group represented by-CO-, in this case, Gx₄As a substituent, Gx₅And Gx₆Each independently represents a hydrogen atom or a substituent. As Gx₄、Gx₅And Gx₆Specific examples of the substituents used in (1) other than Rx₁、Rx₂The substituent(s) other than those usable in (1) above may be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Gx₃Preferably a hydrogen atom or a diethylamine carbonyl group.

In the general formula (1), Qx₁、Qx₂、Qx₃、Qx₄And Qx₅Each independently represents a hydrogen atom or a substituent. As Qx₁、Qx₂、Qx₃、Qx₄And Qx₅Specific examples of the substituents used in (1) other than Rx₁、Rx₂The substituent(s) other than those usable in (1) above may be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Preferably Qx₁、Qx₂、Qx₃、Qx₄And Qx₅Each independently represents a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group (preferably having 1 to 10 carbon atoms), or an aryl group, and more preferably all hydrogen atoms.

Examples of the compound having a structure represented by the general formula (1) include the following compounds.

[ chemical formula 6]

[ chemical formula 7]

[ chemical formula 8]

The compound having a structure represented by the general formula (1) of the present invention can be referred to, for example, Japanese patent application laid-open Nos. 63-226653, 10-193807, 11-78258, 6-250357, 2-155693, 1-110565, 2-668, 2-28264, 2-53865, 2-53866, 1252418, 64-63194, 2-208094, 3-205189, 2-265791, 2-310087, 2-53866, and 2-53866, The synthesis is carried out by a conventionally known method described in each of Japanese patent laid-open Nos. 4-91987, 63-205288, 3-226750, British patent No. 1183515, 4-190348, 63-113077, 3-275767, 4-13774, 4-89287, 7-175187, 10-60296, 11-78258, 2004-138834 and 2006-350300.

These compounds may be used alone or in combination of 2 or more. The content of the compound having a structure represented by general formula (1) is preferably 0.5 to 10% by mass, and more preferably 1 to 8% by mass, based on the entire toner.

In addition to the compound having the structure represented by the general formula (1), a conventional compound may be added as a dye.

As the conventional other coloring matter, a commonly known dye or pigment can be used, and a pigment is preferably used from the viewpoint of light resistance and water resistance. When a dye other than the compound having the structure represented by the general formula (1) is used, the other dye is preferably used in an amount of 0.5 to 1.5 times by mass relative to the compound having the structure represented by the general formula (1).

As other pigments, there can be used: carbon black, aniline blue, calcium oil blue, chrome yellow, ultramarine blue, dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, lampblack, rose bengal, quinacridone, benzidine yellow, c.i. pigment red 57:1, c.i. pigment red 185, c.i. pigment red 238, c.i. pigment yellow 12, c.i. pigment yellow 17, c.i. pigment yellow 180, c.i. pigment yellow 97, c.i. pigment yellow 74, c.i. pigment blue 15:1, c.i. pigment blue 15:3, and the like.

The coloring matter used for obtaining the toner of each color may be used alone in 1 kind or in combination in 2 or more kinds for each color.

(Metal-containing Compound having a Structure represented by the general formula (2))

[ chemical formula 9]

In the general formula (2), R₁Is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group and Rx in the general formula (1)₁、Rx₂The alkyl group used in (1) is the same, and therefore, a detailed description thereof is omitted here.

One or more hydrogen atoms of the alkyl group may be substituted with a substituent. Examples of such substituents include: alkenyl (e.g., vinyl, allyl, etc.), alkynyl (e.g., ethynyl, propargyl, etc.), aryl (e.g., phenyl, naphthyl, 4-octyloxybenzene, etc.), heteroaryl (e.g., furyl, thienyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazolyl, triazinyl, imidazolyl, pyrazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, quinazolinyl, phthalazinyl, etc.), heterocyclic (e.g., pyrrolidinyl, imidazolidinyl, morpholinyl, oxazolidinyl, etc.), alkoxy (e.g., methoxy, ethoxy, propoxy, pentyloxy, hexyloxy, octyloxy, dodecyloxy, cyclopentyloxy, cyclohexyloxy, etc.), aryloxy (e.g., phenoxy, naphthyloxy, etc.), alkylthio (e.g., methylthio, ethylthio, propylthio, pentylthio, hexylthio, octylthio, dodecylthio, cyclopentylthio, etc.), alkylthio (e.g., methylthio, ethylthio, propylthio, pentylthio, hexylthio, octylthio, dodecylthio, cyclopentylthio, etc.) Cyclohexylthio, etc.), arylthio (e.g., phenylthio, naphthylthio, etc.), alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl, etc.), aryloxycarbonyl (e.g., phenoxycarbonyl, naphthyloxycarbonyl, etc.), sulfamoyl (e.g., aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, dodecylaminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl, 2-pyridylaminosulfonyl, etc.), acyl (e.g., acetyl, ethylcarbonyl, propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, phenylcarbonyl, naphthylcarbonyl, etc.), Pyridylcarbonyl and the like), an acyloxy group (e.g., acetoxy, ethylcarbonyloxy, butylcarbonyloxy, octylcarbonyloxy, dodecylcarbonyloxy, phenylcarbonyloxy and the like), an amide group (e.g., methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octylcarbonylamino, dodecylcarbonylamino, phenylcarbonylamino, naphthylcarbonylamino and the like), a carbamoyl group (e.g., aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, octylaminocarbonyl, 2-ethylhexylaminocarbonyl, dodecylaminocarbonyl, phenylaminocarbonyl, naphthylaminocarbonyl, 2-pyridylaminocarbonyl and the like), a urea group (e.g., methylurea group, butylcarbonyl group, octylcarbonyl group, dodecylcarbonyloxy, phenylcarbonyloxy and the like), a urea group (e.g., methylurea group, a methylcarbonylamino group, a methylurea group, a methylcarbonylamino group, a methylurea group, a methylcarbonylamino group, a methylurea group, a methylcarbonylamino group, ethylureido, pentylureido, cyclohexylureido, octylureido, dodecylureido, phenylureido, naphthylureido, 2-pyridylaminoplurourea and the like), sulfinyl (e.g., methylsulfinyl, ethylsulfinyl, butylsulfinyl, cyclohexylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, phenylsulfinyl, naphthylsulfinyl, 2-pyridylsulfinyl and the like), alkylsulfonyl (e.g., methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl and the like), arylsulfonyl (phenylsulfonyl, naphthylsulfonyl, 2-pyridylsulfonyl and the like), amino (e.g., amino, ethylamino, dimethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, naphthylamino, naphthylureido and the like), alkylsulfinyl (e.g., methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, 2-pyridylsulfonyl and the like), alkylsulfonyl, and the like, Dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), cyano group, nitro group, halogen atom (for example, chlorine atom, bromine atom, fluorine atom, iodine atom, etc.), etc., and these groups may be further substituted with the same groups.

As R₁The alkyl group is preferably a C1-4 alkyl group, more preferably a C1-4 linear alkyl group, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

In the general formula (2), R₂Is a hydrogen atom, alkoxycarbonylA group, an arylcarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a nitrophenyl group, a halogen atom, or a cyano group.

More specifically, there may be mentioned: alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octyloxycarbonyl and dodecyloxycarbonyl; arylcarbonyl such as phenylcarbonyl; aryloxycarbonyl groups such as phenoxycarbonyl and naphthyloxycarbonyl; sulfamoyl groups of alkylsulfonylamino groups such as aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl and dodecylaminosulfonyl, and arylsulfonylamino groups such as phenylaminosulfonyl, 3-methyl-4-dodecyloxy-5-tert-butylphenyl aminosulfonyl, naphthylaminosulfonyl and 2-pyridylaminosulfonyl; sulfinyl groups such as methylsulfinyl, ethylsulfinyl, butylsulfinyl, cyclohexylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, phenylsulfinyl, naphthylsulfinyl, 2-pyridylsulfinyl, and the like; alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, 2-ethylhexylsulfonyl and dodecylsulfonyl; arylsulfonyl such as phenylsulfonyl, 4-methylphenylsulfonyl, naphthylsulfonyl and 2-pyridylsulfonyl; acyl groups such as acetyl, ethylcarbonyl, propylcarbonyl, pentylcarbonyl, hexylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl and the like; halogen atom (e.g., chlorine atom, bromine atom, fluorine atom, iodine atom, etc.), cyano group, etc.

As R₂Preferably an alkoxycarbonyl group (preferably 2 to 10 carbon atoms), an arylcarbonyl group (preferably 2 to 10 carbon atoms), an alkylsulfonyl group (preferably 7 to 10 carbon atoms), an arylsulfonyl group (preferably 6 to 10 carbon atoms), an acyl group (preferably 2 to 10 carbon atoms), and a cyano group, more preferably an alkoxycarbonyl group (preferably 2 to 10 carbon atoms), an acyl group (preferably 2 to 10 carbon atoms), and a cyano group, and still more preferably a cyano group.

In the general formula (2), R₃Is a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms.

Here, the aromatic hydrocarbon-containing group having 9 to 120 carbon atoms means R₃In the total number of carbon atoms is 9 to 120 and in R₃Has an aromatic hydrocarbon structure at any position in the above. Examples of the aromatic hydrocarbon structure include an aryl group (e.g., phenyl group, naphthyl group, etc.), and for example, when the aromatic hydrocarbon structure is a phenyl group, R is further formed together with an optional substituent having 3 or more carbon atoms₃. In this case, the substituent may have 3 or more substituents having 1 carbon atom, or may have one or more substituents having 1 carbon atom and 2 carbon atoms. R₃The total number of carbon atoms in (A) is preferably 9 to 40, more preferably 12 to 40, and still more preferably 14 to 30.

As R₃The group represented by the following general formula (3) is preferable.

[ chemical formula 10]

In the general formula (3), L represents a linear or branched alkylene group having 1 to 15 carbon atoms, -SO₂O-、-OSO₂-、-SO₂-、-CO-、-O-、-S-、-SO₂NH-、-NHSO₂A group obtained by combining a plurality of 2-valent linking groups of-CONH-, -NHCO-, -COO-and OOC-, wherein R is a group represented by the general formula (2)₃Adjacent oxygen atoms are bonded.

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

L may have a substituent asExamples of the substituent include R of the general formula (2)₁The substituents used in (1) are the same.

The linking group having a valence of 2 represented by L is preferably an alkylene group or a group containing an alkylene group. The alkylene-containing group may contain an alkylene group at any position of the 2-valent linking group represented by L, and specifically, may be selected from the group consisting of alkylene groups and-SO₂O-、-OSO₂-、-SO₂-、-CO-、-O-、-S-、-SO₂NH-、-NHSO₂-, -CONH-, -NHCO-, -COO-and OOC-in combination with one or more linking groups having a valence of 2.

R₄Represents an aryl group (e.g., phenyl, naphthyl, etc.). Hereinafter, specific examples of the linking group having a valence of 2 represented by L are shown, but the present invention is not limited thereto. In respect of L, in₃Adjacent oxygen atoms or R₄And (4) bonding.

R₃And R₄Examples of the substituent include the same substituents as those used for R1 in the general formula (2).

As L, R₃And R₄Preferred substituents to be substituted in (1) include alkyl (preferably 1 to 20 carbon atoms), alkoxy (preferably 1 to 20 carbon atoms), aryloxy, alkylthio, arylthio, alkoxycarbonyl (preferably 2 to 20 carbon atoms), aryloxycarbonyl, sulfamoyl, acyl, acyloxy, acylamino, alkylaminocarbonyl (preferably 2 to 20 carbon atoms), carbamoyl, alkylsulfonyl, arylsulfonyl, amino, cyano, nitro, and halogen atoms, and more preferably alkyl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, sulfamoyl, acyl, acyloxy, acylamino, and sulfamoylThe carbamoyl group is more preferably an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group or an amido group.

As R₄The phenyl group is preferably a substituted phenyl group, more preferably a phenyl group having an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group or an amide group, and particularly preferably a phenyl group having an alkyl group or an alkoxy group.

As R₃More preferably, it is a group represented by the following general formula (3-1) or (3-2).

[ chemical formula 11]

In the general formula (3-1) and the general formula (3-2), L and X represent the same groups as L and X in the general formula (3), and X independently represents-O-, -NHCO-or COO-, R₅Represents a linear or branched alkyl group having 1 to 30 carbon atoms, and n represents an integer of 0 to 3.

R₅Preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. R₅May have a substituent, and examples of the substituent include R of the general formula (2)₁The substituents used in (1) are the same. R₅The alkyl group is preferably a linear alkyl group, and more preferably contains only carbon atoms and hydrogen atoms.

n is preferably 0 or 1.

L is preferably an alkylene group having 1 to 10 carbon atoms, -R₆-O-radical, -R₆-CO-radical, -R₆-NHCO-yl, -R₆-SO₂-radical, -R₆-COS-yl, -NH-SO₂-radical, -NH-SO₂-R₆-radical or R₆-O-R₆-O-R₆A radical, in which case R₆Is an alkylene group having 1 to 10 carbon atoms. L is more preferably an alkylene group having 1 to 6 carbon atoms or R₆an-O-group (in this case, R6 preferably has 1 to 5 carbon atoms).

In the general formula (2), M is a metal element having a valence of 2. As the metal having a valence of 2, there may be mentioned: iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, tin, and the like. From the viewpoint of reactivity with the compound having the structure represented by general formula (1), M is preferably magnesium, copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, tin (II) chloride, more preferably magnesium, copper, and still more preferably copper (Cu).

The metal-containing compound used in the present invention may have a neutral ligand depending on the central metal, and a representative ligand is H₂O or NH₃。

Examples of the metal-containing compound represented by the structure represented by the general formula (2) include the following structures.

[ chemical formula 12]

[ chemical formula 13]

[ chemical formula 14]

[ chemical formula 15]

These metal-containing compounds may be used alone or in combination of 2 or more. The content of the metal-containing compound is preferably 0.5 to 10% by mass, and more preferably 1 to 8% by mass, based on the entire toner.

The metal-containing compound is preferably synthesized by reacting a metal compound having a valence of 2 with a raw material compound represented by the following general formula (2-1). Examples of the 2-valent metal compound to be used include: metal (II) chloride, metal (II) acetate, metal perchlorate, and the like. The following formula (2-1)R in (1)₁、R₂And R₃And R in the general formula (2)₁、R₂And R₃Synonymously.

Such a specific metal-containing compound can be synthesized by the method described in "chelate chemistry (5) complex chemistry experiment method [ I ] (edited by south Jiangtang)" or the like.

[ chemical formula 16]

The metal-containing compound of the present invention is a compound obtained by coordinating a compound having a structure represented by general formula (1) with a metal-containing compound represented by general formula (2).

The conditions for coordinating the compound having the structure represented by the general formula (1) and the metal-containing compound having the structure represented by the general formula (2) are not particularly limited, and the compound can be obtained by mixing the compound having the structure represented by the general formula (1) and the metal-containing compound represented by the general formula (2) in a solvent, and stirring the mixture for, for example, preferably 50 to 95 ℃, more preferably 60 to 90 ℃, still more preferably 75 to 87 ℃, and preferably 5 to 250 minutes, still more preferably 10 to 60 minutes, and still more preferably 15 to 30 minutes. Specifically, for example, a dispersion liquid containing a metal compound (metal-containing compound fine particle dispersion liquid) is added to a dispersion liquid containing a compound (pigment) having a structure represented by general formula (1) (also simply referred to as "pigment fine particle dispersion liquid" or "pigment dispersion liquid") or a dispersion liquid containing a pigment such as a resin fine particle dispersion liquid containing a pigment or a wax-containing resin fine particle dispersion liquid, whereby the dispersion liquid is temporarily clouded and the dispersion liquid (supernatant liquid) is made transparent by stirring. Thus, the reaction of the dye represented by the general formula (1) and the metal-containing compound represented by the general formula (2) is terminated, and it is considered that a colorant as a reaction compound is formed. As the solvent used in this reaction, a solvent used in the preparation of the toner is preferably used, and as a specific solvent, the description is given in the section of the method for preparing the toner.

< other additives >

The toner base particles may contain other components such as a release agent (wax) and a charge control agent, if necessary.

(mold releasing agent)

As the release agent, various known waxes can be used. Examples of the wax include: polyolefin waxes such as polyethylene wax and polypropylene wax, branched chain hydrocarbon waxes such as microcrystalline wax, long chain hydrocarbon waxes such as paraffin wax and saso wax, dialkyl ketone waxes such as distearyl ketone, carnauba wax, montan wax, behenyl behenate, trimethylolpropane tribehenyl behenate, pentaerythritol tetrabehenyl ester, pentaerythritol diacetate dibehenyl ester, glyceryl behenate, ester waxes such as 1, 18-octadecanediol distearate, tristearyl trimellitate and distearyl maleate, and amide waxes such as ethylenediamine behenamide and trimellitic acid tristearamide. From the viewpoint of fixability, hydrocarbon waxes are preferred.

The content of the release agent is preferably 0.1 to 30 parts by mass, and more preferably 1 to 10 parts by mass, based on 100 parts by mass of the binder resin. These may be used in 1 kind or in combination of 2 or more kinds. The melting point of the release agent is preferably 50 to 95 ℃ from the viewpoint of low-temperature fixability and releasability of the toner in electrophotography.

(Charge control agent)

As the charge control agent constituting the charge control agent particles, various known ones can be used, and those which are dispersible in an aqueous medium can be used. Specifically, there may be mentioned: nigrosine dyes, metal salts of cyclic acids or higher fatty acids, alkoxylated amines, quaternary ammonium compounds, azo metal complexes, metal salicylates, or metal complexes thereof.

[ external additive ]

The external additive is alumina fine particles having a primary particle diameter with a number average particle diameter in the range of 8-50 nm and subjected to hydrophobic surface modification, and is contained in the range of 0.1-2.0 parts by mass relative to 100 parts by mass of the toner matrix particles.

As described above, by using the surface-modified alumina fine particles having a specific particle diameter as the external additive, it is possible to suppress the deterioration of an image due to the low charge amount of the toner containing the colorant having the metal ion and to suppress the decrease of the color reproducibility due to the low refractive index of the alumina fine particles.

(Fine alumina particles)

Aluminum oxide as Al₂O₃The alumina represented by the formula (i) is known as α -type, γ -type, σ -type, a mixture thereof, or the like, and the shape thereof is cubic to spherical according to the control of the crystal system.

Alumina can be prepared by a known method. As a method for producing alumina, bayer process is generally used, and in order to obtain alumina having high purity and a nano size, hydrolysis method (manufactured by sumitomo chemical), vapor phase synthesis method (manufactured by CI chemical corporation), flame hydrolysis method (manufactured by AEROSIL, japan), spark discharge method (manufactured by rocky chemical corporation) and the like can be used.

(particle diameter)

The number average primary particle diameter of the alumina fine particles of the present invention is preferably in the range of 8 to 50nm, and particularly preferably in the range of 10 to 40 nm. When the particle size is larger than 8nm, the effect can be exhibited without burying the surface of the toner matrix, and when the particle size is 50nm or less, the particle size is less affected by the refractive index of the external additive, and the decrease in color reproducibility can be suppressed.

< method for measuring particle diameter >

An SEM photograph of the toner enlarged by 3 ten thousand times was taken using a Scanning Electron Microscope (SEM) "JEM-7401F" (manufactured by japan electronics, inc.), the particle diameter (feret diameter) of the primary particles of the alumina fine particles was measured by observing the SEM photograph, and the average particle diameter was determined by dividing the total value by the number. The particle size is measured by selecting a region in which the total number of particles in the SEM image is about 100 to 200.

(surface modification)

The alumina fine particles of the present invention are preferably those having a hydrophobic surface modification. Specifically, the content of carbon remaining on the surface of the alumina fine particles after surface modification is preferably in the range of 0.5 to 10 mass%, more preferably 1.5 to 5 mass%. When the amount is 0.5 mass% or more, water molecules are less likely to be coordinated to the toner particle surface, and fluctuation of the charge amount under high temperature and high humidity is suppressed. When the amount is 10% by mass or less, the resistance value is not excessively high, and excessive charging can be suppressed.

< method for measuring carbon content >

The measurement of the carbon content remaining on the surface of the alumina fine particles can be performed by the following procedure. (1) Using a Soxhlet extraction apparatus manufactured by BUCHI, 0.7g of hydrophobic alumina fine particle powder was put on a cylindrical filter paper having a diameter of 28mm, and free surface modifier on the hydrophobic alumina fine particle powder was removed under conditions of an extraction time of 60 minutes and a rinsing time of 30 minutes using hexane as an extraction solvent.

(2) The amount of carbon contained in the free surface modifier was determined by a CHN element analyzer (CHN CODER MT-5 (manufactured by YANACO)).

(surface modifier)

As the surface modifier, there can be used: the general coupling agent, silicone oil, fatty acid metal salt, and the like are preferable because silazane, alkoxysilane, and silicone oil, which are generally negatively chargeable, can provide an effect of charge diffusion.

Specific examples of silazanes and alkoxysilanes include: methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, hexamethyldisilazane, tert-butyldimethylchlorosilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, dimethyldichlorosilane, diphenyldimethoxysilane, tetraethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, hexamethyldisilazane, tert-butyldimethylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, gamma-epoxysilane, gamma-glycidoxypropyltrimethoxysilane, dimethyldichlorosilane, dimethyltrimethoxysilane, dimethyldichlorosilane, and dimethyldichlorosilane, and a, Gamma-mercaptopropyltrimethoxysilane and gamma-chloropropyltrimethoxysilane are representative examples.

Among these, in the present invention, the alumina fine particles subjected to hydrophobic surface modification are preferably alumina fine particles subjected to hydrophobic surface modification by a silane coupling agent represented by the following formula (1).

Formula (1): x_n-Si(OR)_m

(wherein X represents an alkyl group having 1 to 16 carbon atoms; R represents a methyl group or an ethyl group; n represents 1 or 2; m represents 2 or 3; and n + m represents 4.)

Such a surface modifier is particularly preferable because it can react with hydroxyl groups on the surface of the alumina fine particles to uniformly coat the matrix and can suppress the coordination of water molecules. Examples thereof include isobutyltrimethoxysilane and octyltriethoxysilane.

Specific examples of the silicone oil which can be used as the surface modifier include: organosiloxane oligomers, cyclic compounds such as octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane, tetramethylcyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane, and linear or branched organosiloxanes. Further, silicone oils modified at least at the terminal with high reactivity, in which a modifying group is introduced into a side chain or one terminal, both terminals, one terminal of a side chain, both terminals of a side chain, or the like, can be used. The type of the modifying group is not particularly limited, and examples thereof include alkoxy groups, carboxyl groups, carbinol, higher fatty acid modification, phenols, epoxy, and methacrylic acid.

Further, for example, silicone oil having a plurality of types of modifying groups such as alkoxy modification may be used. Further, the dimethylsilicone oil and these modified silicone oils, and other surface modifiers may be mixed or used in combination. Examples of the treating agent used in combination include: silane coupling agents, titanate coupling agents, aluminate coupling agents, various silicone oils, fatty acids, fatty acid metal salts, esterified products thereof, rosin acids, and the like.

Examples of the surface modification method include: a dry method such as a spray drying method for spraying a treating agent or a solution containing a treating agent onto particles floating in a gas phase, a wet method for immersing and drying particles in a solution containing a treating agent, a mixing method for mixing a treating agent and particles by a mixer, and the like.

(amount added)

The content of the alumina fine particles is preferably in the range of 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the toner particles. When the amount is 0.1 parts by mass or more, the toner surface can be sufficiently coated and the targeted effect of suppressing the coordination of water molecules can be obtained, and when the amount is 2.0 parts by mass or less, the color reproducibility can be suppressed from being deteriorated without being affected by the refractive index due to the external additive.

(other external additives)

The external additive may contain other known external additives which do not impair the effects of the present invention. In particular, silica particles having a low refractive index are preferable because they pose little risk of deterioration in color reproducibility. In addition, other known external additives may be further contained. As the known external additive, for example, inorganic fine particles, organic fine particles and a lubricant described later can be used.

Examples of the inorganic fine particles include: inorganic oxide fine particles such as titanium oxide fine particles, inorganic stearic acid compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, inorganic titanic acid compound fine particles such as strontium titanate and zinc titanate, and the like. These inorganic fine particles may be subjected to a gloss treatment, a hydrophobic treatment, or the like with a silane coupling agent, a titanium coupling agent, a higher fatty acid, a silicone oil, or the like, for the purpose of improving heat resistance and storage stability, improving environmental stability, or the like.

As the organic fine particles, for example, spherical organic fine particles having a number average primary particle diameter of about 10 to 2000nm can be used. Specifically, organic fine particles based on homopolymers of styrene, methyl methacrylate, or the like, or copolymers thereof can be used.

The lubricant is used to further improve the cleanability and transferability. As the lubricant, for example, a metal salt of a higher fatty acid can be used. Specific examples of the metal salt of a higher fatty acid include: salts of stearic acid with zinc, aluminum, copper, magnesium, calcium, etc., salts of oleic acid with zinc, manganese, iron, copper, magnesium, etc., salts of palmitic acid with zinc, copper, magnesium, calcium, etc., salts of linoleic acid with zinc, calcium, etc., salts of ricinoleic acid with zinc, calcium, etc., and the like.

[ physical Properties of toner for Electrostatic Charge image development ]

The glass transition temperature of the toner of the present invention is preferably in the range of 30 to 65 ℃ from the viewpoint of obtaining low-temperature fixing properties. The glass transition temperature can be determined by the method described.

The average particle diameter of the toner for electrostatic charge image development of the present invention is preferably in the range of 3 to 9 μm, and more preferably in the range of 3 to 8 μm, in terms of volume-based median particle diameter, for example. When the particle size is produced by, for example, an emulsion aggregation method described later, the particle size can be controlled by the concentration of the aggregating agent used, the amount of the organic solvent added, the aggregation time, the composition of the polymer, and the like.

When the volume-based median particle diameter falls within the above range, the transfer efficiency can be improved, the halftone image quality can be improved, and the image quality of thin lines, dots, and the like can be improved.

The volume-based median diameter of the toner particles can be measured and calculated by using a measuring apparatus in which a computer system having data processing software "Sof aware V3.51" and "MULTISIZER 3" (manufactured by BECKMAN COULTER corporation) are connected. Specifically, 0.02g of toner was added to 20mL of a surfactant solution (for the purpose of dispersing toner particles, for example, a surfactant solution obtained by diluting a neutral detergent containing a surfactant component by 10 times with pure water) to prepare a toner dispersion, and then the toner dispersion was ultrasonically dispersed for 1 minute, and the toner dispersion was injected into a beaker containing "ISOTON II" (manufactured by BECKMAN COULTER) in a sample stage by a pipette until the expressed concentration of the measuring apparatus became 8%. Here, by setting the concentration range, a measurement value having reproducibility can be obtained.

In the measuring apparatus, the number of the measured particles is 25000, the pore diameter is 50 μm, the frequency value is calculated by dividing a range of 1 to 30 μm in the measurement range by 256, and the particle diameter of 50% from the larger side of the volume cumulative fraction is set as the volume-based median diameter.

In the toner of the present invention, the average circularity of each toner particle constituting the toner is preferably 0.930 to 1.000, and more preferably 0.940 to 0.995, from the viewpoint of improving transfer efficiency.

In the present invention, the average circularity of toner particles is measured using "FPIA-2100" (manufactured by Sysmex).

Specifically, a sample (toner particles) is mixed with an aqueous solution into which a surfactant is introduced, ultrasonic dispersion treatment is performed for 1 minute to disperse the mixture, then, an image is taken in an HPF (high power image capture) mode under measurement conditions by "FPIA-2100" (manufactured by Sysmex corporation) at an appropriate concentration of 3000 to 10000 HPF detection numbers, circularities of the respective toner particles are calculated from the following formula (T), circularities of the respective toner particles are added, and the sum is divided by the number of the total toner particles to calculate an average circularity.

Formula (T)

Circularity (perimeter of circle having the same projection area as the particle image)/(perimeter of particle projection image)

Method for producing toner for developing electrostatic charge image

The method for producing the toner of the present invention is not particularly limited, and examples thereof include: known methods such as kneading and pulverizing, suspension polymerization, emulsion aggregation, dissolution and suspension, polyester elongation, and dispersion polymerization. Among these, from the viewpoint of uniformity of particle diameter and controllability of shape, the emulsion aggregation method is preferably employed.

< emulsion aggregation method >

The emulsion aggregation method is a method of producing toner particles by mixing a dispersion of binder resin particles (hereinafter, also referred to as "resin fine particles") dispersed with a surfactant and a dispersion stabilizer, if necessary, with a dispersion of pigment particles (hereinafter, also referred to as "pigment fine particles"), aggregating the mixture to a desired toner particle diameter, and further controlling the shape by fusing the binder resin fine particles. Here, the particles of the binder resin may optionally contain a release agent, a charge control agent, and the like.

A preferred method for producing the toner of the present invention is as follows: an example of a case where toner particles having a core-shell structure are obtained using an emulsion aggregation method.

The method for producing the toner for developing a charged image according to the present invention preferably includes a step selected from the following steps.

(1) Process for producing each fine particle dispersion

(1M-1) preparation step of wax-containing 1 st resin microparticle Dispersion which comprises 1 st resin microparticle and wax-containing 1 st resin microparticle dispersed in an aqueous Medium to prepare a Dispersion

(1M-2) a fine resin particle dispersion liquid preparation step of forming fine resin particles 2 based on a2 nd resin in an aqueous medium and dispersing the fine resin particles 2 to prepare a dispersion liquid

(1U) wax-containing 1 st and 2 nd resin fine particle dispersion liquid preparation step of preparing wax-containing 1 st and 2 nd resin fine particle dispersion liquid by dispersing wax-containing 1 st and 2 nd resin fine particles containing 1 st resin, 2 nd resin and wax in an aqueous medium

(1A) A pigment microparticle dispersion (pigment dispersion) preparation step of dispersing pigment microparticles based on a pigment in an aqueous medium to prepare a dispersion

(1B) A step for preparing a metal compound-containing fine particle dispersion (metal compound-containing dispersion) in which metal compound-containing fine particles are dispersed in an aqueous medium to prepare a dispersion

(1C) A shell resin fine particle dispersion liquid preparation step of forming shell resin fine particles based on a shell resin in an aqueous medium and dispersing the shell resin fine particles to prepare a shell resin fine particle dispersion liquid

(2) Mixing step of pigment Fine particle Dispersion and resin Fine particle Dispersion (No. 1 particle (core particle) Forming step)

(2M-1) a1 st particle formation step of mixing the wax-containing 1 st resin fine particle dispersion, the 2 nd resin fine particle dispersion and the pigment fine particle dispersion in an aqueous medium to aggregate the wax-containing 1 st resin fine particles, the 2 nd resin fine particles and the pigment fine particles to form 1 st particles (core particles)

(2U) the 1 st particle formation step of mixing the wax-containing 1 st and 2 nd fine resin particle dispersions and the fine pigment particle dispersion in an aqueous medium to aggregate the wax-containing 1 st and 2 nd fine resin particles and the fine pigment particles to form the 1 st particles (core particles)

(3) Forming a core-shell structure by coating the 1 st particles

(3M) a shell-forming step of adding a shell resin fine particle dispersion to an aqueous medium in which the 1 st particles (core particles) are dispersed to aggregate the shell resin fine particles on the surface of the 1 st particles (core particles) and fuse the particles to form the 2 nd particles having a core-shell structure

(4) Mixing a metal compound fine particle dispersion with a dispersion containing the 1 st or 2 nd particles to aggregate the 1 st or 2 nd particles and the metal compound fine particles to form toner base particles

(5) Aging step for adjusting the shape of toner matrix particles by aging with heat energy

(6) A cleaning step of filtering the 1 st particles or the 2 nd particles (toner base particles) from the dispersion (aqueous medium) of the toner base particles and removing the surfactant and the like from the toner base particles

(7) Drying step of drying toner base particles subjected to cleaning treatment

(8) And an external additive adding step of adding an external additive to the toner base particles subjected to the drying treatment.

As the toner for electrostatic charge image development of the present invention, it is preferable to use a crystalline polyester resin as the 1 st resin and a non-crystalline polyester resin as the 2 nd resin. In this case, since the toner for electrostatic charge image development may have a single-layer structure, the steps (1) to (4) preferably include the steps (1A), (1B), (2U), and (4).

That is, the method for producing the toner for electrostatic charge image development preferably includes:

a step (a) of mixing a dispersion liquid containing a binder resin at least containing a crystalline polyester resin with a dispersion liquid containing a pigment represented by the general formula (1);

and (b) mixing a dispersion containing the metal-containing compound represented by the general formula (2) with the dispersion obtained in the step (1).

If necessary, the 3 rd resin fine particles (amorphous polyester resin or styrene-acrylic resin) may be further coated as a shell.

Further, as the toner for electrostatic charge image development, in the case of using a styrene-acrylic resin as the 1 st resin and a crystalline polyester resin as the 2 nd resin, it is preferable to have a core-shell structure, and in this case, it is preferable to have: (1M-1), (1M-2), (1A), (1B), (1C), (2M), (3) and (4).

In the present invention, the pigment and the metal-containing compound are preferably added to the dispersion liquid not at the same time when the toner particles are formed, but after the pigment-containing particles are aggregated and grown, the metal-containing compound is added. This can disperse charges and further exert an effect as a charge control agent.

< external addition treatment >

For the mixing treatment of the external additive to the toner base particles, a mechanical mixing device may be used. As the mechanical mixing device, there can be used: HENSCHEL mixer, NAUTA mixer, TURBULER mixer, etc. Among these, the mixing treatment may be carried out by using a mixing device such as a HENSCHEL mixer which can apply a shearing force to the particles to be treated, and by increasing the mixing time or the rotational speed of the stirring blade. In the case of using a plurality of external additives, all of the external additives are mixed together with the toner particles or the mixing process is performed in a plurality of times depending on the external additives.

The mixing method of the external additive can control the degree of pulverization and the adhesion strength of the external additive by controlling the mixing intensity, that is, the peripheral speed of the stirring blades, the mixing time, the mixing temperature, and the like, using the mechanical mixing device.

[ developer ]

The toner of the present invention can be used as a one-component developer, but can be mixed with a carrier and preferably used as a two-component developer. The carrier preferably has a carrier-coating resin on a carrier core (carrier core material).

(Carrier core)

Examples of the carrier core (magnetic particles) used in the present invention include: iron powder, magnetite, various ferrite particles, or a dispersion of these particles in a resin. Preferred are magnetite and various ferrite particles. As the ferrite, preferred are: ferrite containing a heavy metal such as copper, zinc, nickel, or manganese, and light metal ferrite containing an alkali metal or an alkaline earth metal.

In addition, Sr is preferably contained as the core material. By containing Sr, the unevenness of the surface of the core material can be increased, and the surface can be easily exposed even when resin is applied, and the resistance of the carrier can be easily adjusted.

(particle diameter of Carrier)

The volume average particle diameter of the carrier is preferably 10 to 100 μm, and more preferably 20 to 80 μm. The volume average particle diameter of the carrier can be measured typically by a laser diffraction particle size distribution measuring apparatus "helos (helos) equipped with a wet disperser (manufactured by SYMPATEC corporation).

(Carrier-coated resin)

Suitable resins for forming the coating layer of the carrier include: polyolefin resins such as polyethylene, polypropylene, chlorinated polyethylene, and chlorosulfonated polyethylene; polyvinyl and polyvinylidene resins such as polyacrylates such as polystyrene and polymethyl methacrylate, polyacrylonitriles, polyvinyl acetates, polyvinyl alcohols, polyvinyl butyrals, polyvinyl chlorides, polyvinyl carbazoles, polyvinyl ethers, and POKETONE; copolymers such as chlorinated vinyl-vinyl acetate copolymer and styrene-acrylic acid copolymer; polysiloxane resins containing organosiloxane bonds or modified resins thereof (e.g., modified resins based on alkyd resins, polyester resins, epoxy resins, polyurethanes, etc.); fluorine resins such as polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, and polychlorotrifluoroethylene; a polyamide; a polyester; a polyurethane; a polycarbonate; amino resins such as urea-formaldehyde resins; epoxy resins, and the like.

In particular, a polyacrylate resin is preferable, and a resin containing an alicyclic methacrylate monomer having a low moisture absorption property is preferable because fluctuation in charge amount due to environmental difference and burying of alumina particles due to impact between the toner and the carrier are suppressed as described above.

The alicyclic methacrylate monomer is preferably a cycloalkyl group having 5 to 8 carbon atoms from the viewpoints of mechanical strength, environmental stability of charge amount (environmental difference in charge amount is small), ease of polymerization, and ease of handling. The alicyclic methacrylate monomer is preferably at least one selected from the group consisting of cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, and cyclooctyl (meth) acrylate. Among them, cyclohexyl (meth) acrylate is preferably contained from the viewpoint of mechanical strength and environmental stability of charge amount.

The proportion of the copolymer of the alicyclic methacrylate monomer is preferably 50% or more, and more preferably 75% or more.

(coating method)

Specific examples of the method for producing the coating layer include a wet coating method and a dry coating method. Hereinafter, each method will be described, and a dry coating method, which is a method particularly suitable for the present invention, will be described in detail.

The wet coating method includes the following methods.

(1) Fluidized bed type spray coating method

A method for preparing a coating layer by dissolving a coating resin in a solvent to obtain a coating liquid, spray-coating the coating liquid on the surface of magnetic particles using a fluidized bed, and drying the coating liquid

(2) Immersion coating method

Method for preparing coating layer by impregnating magnetic particles in coating liquid obtained by dissolving coating resin in solvent, and drying

(3) Polymerization process

A method in which magnetic particles are immersed in a coating solution obtained by dissolving a reactive compound in a solvent to perform a coating treatment, and then polymerization is performed by heating or the like to prepare a coating layer.

(Dry coating method)

It comprises the following steps: a method for producing a coating layer, which comprises adhering fine resin particles to the surface of particles to be coated, and then applying a mechanical impact to melt or soften and fix the fine resin particles adhering to the surface of the particles to be coated. The carrier core particles, the resin, the low-resistance fine particles, and the like are stirred at a high speed using a high-speed stirring mixer capable of imparting a mechanical impact force under non-heating or heating, and the impact force is repeatedly imparted to the mixture, thereby preparing a carrier which is dissolved or softened and fixed to the surfaces of the magnetic particles. The coating conditions are preferably 80 to 130 ℃ in the case of heating, and are preferably 10m/s or more in the case of heating and 5m/s or less in the case of cooling in order to suppress aggregation of carrier particles with each other as the wind speed for generating an impact force. The time for applying the impact force is preferably 20 to 60 minutes.

A method of exposing the core material by peeling off the resin of the convex portion of the core material by applying stress to the carrier in the resin application step or the step after the resin application will be described. In the resin coating step by the dry coating method, the resin may be peeled off by using the wind speed at the time of cooling for high-speed shearing while the heating temperature is reduced to 60 ℃ or lower. The step after coating may be performed by any apparatus capable of performing forced stirring, and examples thereof include: TURBULLER, ball mill, vibration mill, etc. are stirred and mixed.

Next, as a method of exposing the core material by applying heat and impact to the coating resin to move the resin present on the surface of the convex portion toward the concave portion, it is effective to extend the time for applying the impact force. Specifically, it is preferably 1 half hour or more.

[ examples ]

The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the examples, "part" or "%" is used, and unless otherwise specified, "part by mass" or "% by mass" is used.

Preparation of amorphous polyester resin (A1)

316 parts by mass of a bisphenol A propylene oxide 2-mole adduct, 65 parts by mass of terephthalic acid, 49 parts by mass of fumaric acid, and 2 parts by mass of titanium tetraisopropoxide as a polycondensation catalyst were introduced into a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet pipe in 10 portions, and water produced was distilled off under a nitrogen stream at 200 ℃ to react for 10 hours.

Then, the reaction mixture was reacted under a reduced pressure of 13.3kPa (100mmHg) and taken out at a time point at which the softening point became 104 ℃. This was made into an amorphous polyester resin (a 1). The glass transition temperature of the amorphous polyester resin (a1) measured by DSC method was 45 ℃.

Preparation of crystalline polyester resin (B1)

Into a flask, 10 parts by mass of 1, 9-nonanediol, 10 parts by mass of 1, 10-dodecanedioic acid, and a catalyst Ti (OBu)₄(0.014 mass% relative to the polycarboxylic acid component), the pressure of the air in the vessel was reduced by a pressure reduction operation, and the mixture was refluxed at 180 ℃ for 6 hours by mechanical stirring while being kept in an inert atmosphere by nitrogen gas. Then, unreacted monomer components were removed by distillation under reduced pressure, and the mixture was gradually heated to 220 ℃ and stirred for 12 hours to obtain a viscous state, and then a sample was taken to obtain a crystalline polyester resin (B1). The acid value of the crystalline polyester resin (B1) was 23 mgKOH/g. The obtained crystalline polyester resin (B1) had a melting temperature (Tc) of 78 ℃, a weight-average molecular weight of 12000 and a number-average molecular weight of 4000.

Preparation of Fine wax-containing resin particle Dispersion (1)

Crystalline polyester resin (B1) (90 parts by mass) and amorphous polyester resin (A1) (510 parts by mass) were dissolved in 2400 parts by mass of ethyl acetate (manufactured by Kanto chemical Co.) with stirring, and then 30 parts by mass of paraffin wax (melting point: 73 ℃ C.) as a mold release agent was added and dissolved by heating. Next, 2400 parts by mass of a 0.26% concentration sodium lauryl sulfate solution prepared in advance were mixed, and ultrasonic dispersion was performed at V-LEVEL 300. mu.A for 30 minutes by an ultrasonic homogenizer "US-150T" (manufactured by NIHONSEIKI KAISHA) while stirring, and then ethyl acetate was completely removed while stirring under reduced pressure for 6 hours by using a diaphragm vacuum pump "V-700" (manufactured by BU CHI) in a state of being heated at 50 ℃ to prepare a wax-containing resin fine particle dispersion (1) having a volume-based median particle diameter (D50) of 250nm and a solid content of 20% by mass.

Preparation of colorant particle Dispersion

< Synthesis of coloring matter >

< Synthesis of exemplary Compound (1-1) >

[ chemical formula 17]

In intermediate 1: 1.93g, intermediate 2: to 1.53g, toluene was added with stirring: 50mL and morpholine: 0.53g, heated to reflux, dehydrated through an ester tube and reacted for 8 hours. After the reaction is finished, concentrating the reaction solution, purifying by column chromatography, and recrystallizing by using an ethyl acetate/hexane mixed solvent to obtain DX-1: 2.71 g. Through MASS,¹The product was confirmed to be the target product by H-NMR and IR spectroscopy. Purity of the exemplary Compound 1-1 obtained by¹As a result of analysis by H-NMR, 98% was obtained. When the visible light absorption spectrum of the exemplified compound 1-1 was measured (solvent: ethyl acetate), the maximum absorption wavelength: 535nm, molar absorptivity: 71000 (L/mol. cm).

Hereinafter, compounds having a structure represented by general formula (1) used in examples were synthesized in the same manner as described above, using the corresponding raw materials (changing the corresponding substituents). Each purity is obtained by¹The H-NMR analysis showed that the concentration was 95% or more.

< Synthesis of Metal-containing Compound (exemplary Compounds 2 to 8 (Metal: Cu) >

[ chemical formula 18]

(Synthesis of Compound B)

In a 500mL 3-necked flask, 90g of compound a, 21.5g of cyanoacetic acid, 1.31g of p-toluenesulfonic acid monohydrate, and 300mL of toluene were added, and dehydration was performed using an ester tube, followed by heating and refluxing for 2 hours, and after removing the solvent by distillation under reduced pressure, 500mL of acetone was added and recrystallization was performed, thereby obtaining 94.4g of compound B.

(Synthesis of Compound C)

In a 100mL 3-necked flask, 5g of Compound B, 25mL of toluene, 3.3g of triethylamine, and 2.42g of calcium chloride were added, the mixture was heated to 80 ℃ and stirred. After the internal temperature reached 80 ℃, 2.1g of acetyl chloride was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was cooled, separated with dilute hydrochloric acid, and then the solvent was distilled off while the pH was kept neutral with pure water. Toluene (50 mL) and ethyl acetate (50 mL) were added and the mixture was recrystallized to obtain compound C4.3 g.

(Synthesis of Metal-containing Compound 2-8)

In a 200mL 3-necked flask, 2g of Compound C and 80mL of acetone were added, and the mixture was heated to an internal temperature of 55 ℃ and stirred. Then, 0.55g of copper acetate 1 hydrate was dissolved in 5mL of a solvent (MeOH/water-5/1), and the solution was added dropwise over 30 minutes. After completion of the dropwise addition, the precipitated solid was filtered to obtain 1.4g of a metal-containing compound (exemplified compounds 2 to 8 (metal: Cu)). The transmittance at 500nm of the obtained exemplified compounds 2 to 8 (metal: Cu) was 98% (solvent: THF), and the purity was 98%.

The metal-containing compounds represented by the general formula (2) used in the examples were synthesized in the same manner as in the above-described method using the corresponding raw materials (with the corresponding substituents changed). The purity of each metal-containing compound was confirmed to be 90% or more by measuring the transmittance at 500 nm.

< preparation of pigment Dispersion >

Preparation of pigment Dispersion (1) [ (Process of 1A) ]

An aqueous surfactant solution was prepared by dissolving 63 parts by mass of sodium n-dodecyl sulfate in 880 parts by mass of ion-exchanged water with stirring. To this surfactant aqueous solution, 1 to 180 parts by mass of the exemplified compound as a coloring matter and 100 parts by mass of quinacridone were slowly added, followed by dispersion treatment using "clear IX (registered trademark) W MOTION CLM-0.8" (manufactured by M TECHNIQUE corporation), to prepare a coloring matter dispersion liquid (1) having a solid content of particles in which the coloring matter (exemplified compound 1 to 1) is dispersed of 16 mass%.

The particle diameter of the pigment particles in the pigment dispersion (1) was 260nm when the volume-based median particle diameter was measured.

The volume-based median particle diameter was measured by using "MICROTRAC UPA-150" (manufactured by HONEYWELL Co., Ltd.) under the measurement conditions of a sample refractive index of 1.59, a sample specific gravity of 1.05 (in terms of spherical particles), a solvent refractive index of 1.33, a solvent viscosity of 0.797(30 ℃) and 1.002(20 ℃) by adding ion-exchanged water to a measurement cell and adjusting the 0 point.

Preparation of Metal Compound-containing Dispersion (1) [ Process of 1B ]

89 parts by mass of the metal-containing compound (compound No. 2 to 8 (metal: Cu)) shown in Table 1 was added to a solution prepared by dissolving 16 parts by mass of sodium lauryl sulfate in 530 parts by mass of ion-exchanged water, and stirring and ultrasonic waves were applied thereto to prepare a dispersion of the metal-containing compound (1) having a solid content of 14 mass%. The volume-based median particle diameter was 270 nm.

Preparation of toner mother particles

< production of toner mother particle (1) >

In a 5L stainless steel reactor equipped with a stirrer, a condenser and a temperature sensor, 2250 parts by mass of the wax-containing resin fine particle dispersion (1), 1400 parts by mass of ion-exchanged water and 138 parts by mass of the pigment dispersion (1) were charged, and while stirring, the pH was adjusted to 10 using a 5 mol/L aqueous sodium hydroxide solution. Then, an aqueous magnesium chloride solution prepared by dissolving 60 parts by mass of magnesium chloride hexahydrate in 60 parts by mass of ion-exchanged water was added dropwise over 10 minutes under stirring, the internal temperature was raised to 75 ℃, the particle diameter was measured using "MULTIPISIZER 3" (manufactured by BECKMAN COULTER Co., Ltd., pore diameter; 50 μm), and 125 parts by mass of the metal-containing compound dispersion (1) was added dropwise at the time when the average particle diameter reached 6.5 μm. Then, at a point of time when the supernatant of the reaction solution became transparent (reaction of the dye and the metal-containing compound was completed to form a reaction compound), 50 parts by mass of sodium chloride was dissolved in 200 parts by mass of ion-exchanged water, and the mixture was further heated and stirred, and the internal temperature was cooled to 25 ℃ at a point of time when the average circularity became 0.960 using a flow particle imaging apparatus "FPIA-2100" (manufactured by Sysmex). The volume-based median particle diameter (D50) of the obtained toner base particles (1) was 6.1 μm.

< Cooling Process >

Then, the resultant was cooled at a cooling rate of 10 ℃/min using "FPIA-3000" at a time point when the shape factor became 0.970, to obtain a toner base particle dispersion (1).

< filtration/cleaning step and drying step >

Then, the mixture was filtered and washed thoroughly with ion-exchanged water. Subsequently, the resultant was dried at 40 ℃ to obtain toner base particles (1). The volume-based median particle diameter of the obtained toner base particles (1) was 6.0 μm, and the average circularity was 0.972.

< production of toner base particles 2 to 9, 12 to 15, and 18 to 26 >

In the preparation of the toner base particles 1, toner base particles 2 to 9, 12 to 15, and 18 to 26 were prepared by changing the example compound 1-1 and the metal-containing compound 2-8 as pigments as shown in Table I.

In the preparation of the toner base particles 18, 180 parts by mass of a quinacridone pigment having a structure shown below is used instead of 1 to 180 parts by mass of the compound exemplified as a coloring matter. In addition, in the preparation of the toner base particles 18 and 19, a dispersion liquid of a metal-containing compound is not added.

[ chemical formula 19]

< preparation of toner mother particle 10 >

Preparation of amorphous polyester resin (A2)

Then, the reaction mixture was reacted under a reduced pressure of 13.3kPa (100mmHg) and taken out at a time point at which the softening point became 104 ℃. This was made into an amorphous polyester resin (a 2). The glass transition temperature of the amorphous polyester resin (a2) measured by DSC method was 29 ℃.

In the preparation of the toner base particles 1, the compounds having the structures represented by the general formulae (1) and (2) were changed to the compounds represented in table I, and the amorphous polyester (a1) was changed to (a2) to prepare toner base particles 10.

< preparation of toner mother particle 11 >

Preparation of amorphous polyester resin (A3)

316 parts by mass of a bisphenol A propylene oxide 2-mole adduct, 95 parts by mass of terephthalic acid, 19 parts by mass of fumaric acid, and 2 parts by mass of titanium tetraisopropoxide as a polycondensation catalyst were introduced into a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet pipe in 10 portions, and water produced was distilled off under a nitrogen stream at 200 ℃ to react for 10 hours.

Then, the reaction mixture was reacted under a reduced pressure of 13.3kPa (100mmHg) and taken out at a time point at which the softening point became 104 ℃. This was made into an amorphous polyester resin (a 3). The glass transition temperature of the amorphous polyester resin (a3) measured by the DSC method was 65 ℃.

< preparation of toner mother particles 16 >

Preparation of styrene acrylic resin (C1)

(1-1) stage 1 polymerization

An anionic surfactant solution prepared by dissolving 2.0 parts by mass of an anionic surfactant "sodium lauryl sulfate" in 2900 parts by mass of ion-exchanged water was charged in advance into a reaction vessel equipped with a stirrer, a temperature sensor, a temperature controller, a condenser and a nitrogen gas introducing device, and the internal temperature was raised to 80 ℃ while stirring at a stirring speed of 230rpm under a nitrogen gas flow. To the anionic surfactant solution, 9.0 parts by mass of a polymerization initiator "potassium persulfate (KPS)" was added, and after the internal temperature was set to 78 ℃, the solution (1) was added dropwise over 3 hours.

The solution (1) comprises:

540 parts by mass of styrene

154 parts by mass of n-butyl acrylate

77 parts by mass of methacrylic acid

17 parts by mass of n-octyl mercaptan

After completion of the dropwise addition, polymerization was carried out by heating and stirring at 78 ℃ for 1 hour (polymerization in stage 1), thereby preparing a dispersion of "resin fine particles (c 1)".

(1-2) polymerization in stage 2: formation of intermediate layer

In a flask equipped with a stirring device,

the solution (2) comprises:

94 parts by mass of styrene

60 parts by mass of n-butyl acrylate

11 parts by mass of methacrylic acid

5 parts by mass of n-octyl mercaptan

To the solution (2), 51 parts by mass of paraffin wax (melting point: 73 ℃ C.) as a mold release agent was added, and the mixture was heated and dissolved at 85 ℃ to prepare a monomer solution [2 ].

On the other hand, a surfactant solution obtained by dissolving 2 parts by mass of an anionic surfactant "sodium lauryl sulfate" in 1100 parts by mass of ion-exchanged water was heated at 90 ℃. To this surfactant solution, 28 parts by mass of the dispersion of the "fine resin particles (c 1)" was added based on the solid content of the fine resin particles (c1), and then the monomer solution [2] was mixed and dispersed for 4 hours by a mechanical disperser "CLEARMIX (registered trademark)" (manufactured by mitechnique corporation) having a circulation path, thereby preparing a dispersion containing emulsified particles having a dispersed particle diameter of 350 nm. To this dispersion, an initiator aqueous solution obtained by dissolving 2.5 parts by mass of potassium persulfate (KPS) as a polymerization initiator in 110 parts by mass of ion-exchanged water was added, and the system was heated and stirred at 90 ℃ for 2 hours to carry out polymerization (stage 2 polymerization), thereby preparing a dispersion of "resin fine particles (c 11)".

(1-3) stage 3 polymerization: formation of the outer layer

To the dispersion of the "resin fine particles (c 11)", an aqueous initiator solution obtained by dissolving 2.5 parts by mass of potassium persulfate (KPS (44) JP 2015-161825A 2015.9.710203040) as a polymerization initiator in 110 parts by mass of ion-exchanged water was added, and the solution (3) was added dropwise over 1 hour at a temperature of 80 ℃.

The solution (3) comprises:

230 parts by mass of styrene

100 parts by mass of n-butyl acrylate

5.2 parts by mass of n-octyl mercaptan

After the completion of the dropwise addition, the mixture was heated and stirred for 3 hours to effect polymerization (stage 3 polymerization). Then, the mixture was cooled to 28 ℃, ion-exchanged water was added thereto, and the amount of solid components was adjusted so as to be 30% by mass, thereby preparing an amorphous "styrene acrylic resin (C1) dispersion 1".

Preparation of Dispersion 1 of amorphous polyester resin (A1)

100 parts by mass of the obtained amorphous polyester resin (a1) was dissolved in 400 parts by mass of ethyl acetate. Subsequently, 25 parts by mass of a 5.0 mass% aqueous sodium hydroxide solution was added to form a resin solution. This resin solution was put into a vessel equipped with a stirring device, and 638 parts by mass of a 0.26 mass% aqueous solution of sodium lauryl sulfate was dropwise mixed over 30 minutes while stirring the resin solution. After the sodium lauryl sulfate aqueous solution was completely dropped, an emulsion in which resin solution particles were uniformly dispersed was obtained. Then, the emulsion was heated to 40 ℃ and ethyl acetate was distilled off under reduced pressure of 150hPa using a diaphragm vacuum pump "V-700" (manufactured by BUCHI) to obtain "dispersion 1 of amorphous polyester resin (A1)" having a solid content of 20 mass%.

Preparation of Dispersion 1 of crystalline polyester resin (B1)

In the preparation of the dispersion 1 of the amorphous polyester resin (a1), except that the crystalline polyester resin (B1) was used in place of the amorphous polyester resin (a1), "dispersion 1 of the crystalline polyester resin (B1") was prepared in the same manner.

(preparation of toner mother particle 16)

Into a reaction vessel equipped with a stirrer, a temperature sensor, and a condenser, 11125 parts by mass of a styrene acrylic resin (C1) dispersion, 1337.5 parts by mass of a crystalline polyester resin (B1) dispersion, and 1380 parts by mass of ion-exchanged water were charged, and then 5 mol/l aqueous sodium hydroxide solution was added to adjust the pH to 10 at 25 ℃. Then, 140 parts by mass of "pigment fine particle dispersion 1" was charged.

Next, 60 parts by mass of magnesium chloride was dissolved in 60 parts by mass of ion-exchanged water, and the resulting aqueous solution was added at 30 ℃ for 10 minutes while stirring. Then, the temperature was raised after leaving for 3 minutes, and the system was heated to 80 ℃ over 60 minutes, and the particle growth reaction was continued while keeping at 80 ℃. In this state, the particle size of the associated particles was measured by "coulter size r 3" (manufactured by coulter beckman corporation), 225 parts by mass of the "dispersion of the amorphous polyester resin (a1) was added at a time point when the median particle size (D50) on a volume basis became 6.0 μm, and 120 parts by mass of the dispersion of the metal-containing compound was added dropwise at a time point when the supernatant of the reaction solution became transparent. At the time point when the supernatant of the reaction solution became transparent (reaction of the dye and the metal-containing compound was completed to form a reaction compound), an aqueous solution prepared by dissolving 53 parts by mass of sodium chloride in 210 parts by mass of ion-exchanged water was added to stop the particle growth.

Further, the temperature was increased, the mixture was heated and stirred at 90 ℃ to fuse the particles, and the mixture was cooled at 30 ℃ at the time point when the average circularity of the toner became 0.945 (number of detected HPFs: 4000) using "FPIA-2100" (manufactured by Sysmex) which is a device for measuring the average circularity of toner ", to prepare" a dispersion of toner base particles 16 ". The volume-based median diameter (D50) of the obtained toner base particles 16 was 6.2 μm.

< preparation of toner mother particle 17 >

(preparation of toner mother particle 17)

In a reaction vessel equipped with a stirrer, a temperature sensor, and a condenser, 11275 parts by mass of a styrene acrylic resin (C1) dispersion, 1337.5 parts by mass of a crystalline polyester resin (B1) dispersion, and 1380 parts by mass of ion-exchanged water were charged, and then 5 mol/l aqueous sodium hydroxide solution was added to adjust the pH to 10 at 25 ℃. Then, 140 parts by mass of "pigment fine particle dispersion 1" was charged.

Next, 60 parts by mass of magnesium chloride was dissolved in 60 parts by mass of ion-exchanged water, and the resulting aqueous solution was added at 30 ℃ for 10 minutes while stirring. Then, the temperature was raised after leaving for 3 minutes, and the system was heated to 80 ℃ over 60 minutes, and the particle growth reaction was continued while keeping at 80 ℃. In this state, the particle size of the associated particles was measured by "coulter size r 3" (manufactured by coulter beckman corporation), and 120 parts by mass of the metal compound-containing dispersion was added dropwise at a point when the median particle size (D50) on a volume basis became 6.0 μm. At the time point when the supernatant of the reaction solution became transparent (reaction of the dye and the metal-containing compound was completed to form a reaction compound), an aqueous solution prepared by dissolving 53 parts by mass of sodium chloride in 210 parts by mass of ion-exchanged water was added to stop the particle growth.

Further, the particles were fused by heating and stirring at 90 ℃ and cooled at 30 ℃ at the time point when the average circularity of the toner became 0.945 (the number of detected HPFs was 4000) using "FPIA-2100" (manufactured by Sysmex) as a device for measuring the average circularity of the toner ", thereby preparing" a dispersion of toner base particles 17 ". The volume-based median diameter (D50) of the toner base particles 17 thus obtained was 6.1 μm.

[ external additive ]

Preparation of external additive 1

(preparation of alumina Fine particles)

The alumina fine particles can be produced by a known method, and the present invention will be specifically described below by referring to examples, but the present invention is not limited thereto.

As an example of the method for producing alumina of the present invention, a known burner apparatus described in example 1 of specification of european patent No. 0585544 is prepared by referring to the contents of japanese patent laid-open No. 2012-224542.

Specifically, aluminum trichloride (AlCl)₃)320kg/h were evaporated at about 200 ℃ in an evaporator, and the chloride vapors were passed through a mixing chamber of a burner by means of nitrogen. Here, the gas stream is brought into contact with 100Nm of hydrogen³H and air 450Nm³Mixed and fed to the flame through a central tube (diameter 7 mm). As a result, the burner temperature was 230 ℃ and the discharge velocity of the tube was about 35.8 m/s. Hydrogen 0.05Nm³As jacket type gas and supplied through the outside tube. The gases are combusted in the reaction chamber and cooled to about 110 ℃ in a downstream condensation zone. Thereby, the primary particles of alumina are aggregated. At the same time, the obtained alumina particles are separated in a filter or a cyclone separator from the generated hydrochloric acid-containing gas, and the powder with wet air is treated at about 500 to 700 ℃ to remove the adhesive chloride. Thereby, the alumina fine particles 1 can be obtained.

(surface hydrophobization treatment)

The alumina fine particles 1 thus obtained were charged into a reaction vessel, and 100g of the alumina powder was added with a substance obtained by diluting 20g of a hydrophobizing agent octyltriethoxysilane with 60g of hexane while stirring the powder with a rotary blade under a nitrogen atmosphere, and after heating and stirring at 200 ℃ for 120 minutes, the mixture was cooled with condensed water to obtain an external additive 1.

As a result of measurement by the measurement method, the carbon content after surface modification was 3.0 mass%.

Preparation of external additives 2 to 4, 13 and 14

In the preparation of the external additive 1, the external additive particles 2 to 4, 13 and 14 are prepared by changing the reaction conditions, for example, the flame temperature, the hydrogen or oxygen content, the quality of aluminum trichloride, the residence time in the flame or the length of the coagulation zone.

Preparation of external additives 5 to 10 and 15

In the preparation of the external additive 1, the types and amounts of the surface modifiers described in the examples table were changed to prepare external additive particles 5 to 10.

The external additive particles that have not been surface-modified are referred to as external additives 15.

Preparation of external additive 11

100 parts by mass of silica powder having a number-average primary particle diameter of 15nm was charged into a reactor, stirred in a nitrogen atmosphere, and 3.0g of water was sprayed, 10 parts by mass of isobutyltrimethoxysilane and 1.0 part by mass of diethylamine as hydrophobizing agents were sprayed thereto, heated and stirred at 180 ℃ for 1 hour, and then cooled to obtain an external additive 11.

Preparation of external additive 12

100 parts by mass of titanium dioxide powder having a number average primary particle diameter of 15nm was charged into a reactor, stirred in a nitrogen atmosphere, and 3.0g of water was sprayed, 10 parts by mass of isobutyltrimethoxysilane and 1.0 part by mass of diethylamine as hydrophobizing agents were sprayed thereto, heated and stirred at 180 ℃ for 1 hour, and then cooled to obtain external additive 12.

[ preparation of developer ]

Preparation of toner particles 1

(external additive addition Process)

To the toner base particles 1, 10.6 parts by mass of an external additive and 0.5 part by mass of hydrophobic silica "RY 50 (manufactured by japan AEROSIL corporation)") were added and mixed for 20 minutes by a HENSCHEL mixer to prepare toner particles 1.

Preparation of toner particles 2 to 26

In the preparation of toner particles 1, toner base particles and external additives were changed as described in table I to prepare toner particles 2 to 26.

(glass transition temperature Tg)

The prepared toner particles 1 to 26 were measured for glass transition temperature by the differential scanning calorimetry. The results are shown in Table I.

In table I, materials shown below were used.

Isobutyl silane: isobutyl trimethoxy silane

Octyl silane: n-octyl triethoxysilane

C16 silane: n-hexadecyltrimethoxysilane

HMDS: hexamethyldisilazane

PDMS: dimethylsilicone oil (Mw 9900)

In addition, the following abbreviations are used in the tables.

PES: amorphous polyester resin

StAc/PES: non-crystalline polyester resin/styrene acrylic resin

StAc: styrene acrylic resin

Preparation of Carrier particles

(preparation of Carrier core particle)

To become MnO: 35 mol%, MgO: 14.5 mol% and Fe₂O₃: 50 mol% and SrO: the raw materials were weighed to 0.5 mol%, mixed with water, and then pulverized for 5 hours by a wet media mill to obtain a slurry.

The obtained slurry was dried by a spray dryer to obtain spherical particles. After adjusting the particle size, the particles were pre-fired by heating at 950 ℃ for 2 hours. After being pulverized by a wet ball mill for 1 hour using stainless steel balls having a diameter of 0.3cm, the resultant was further pulverized for 4 hours using zirconia balls having a diameter of 0.5 cm. PVA as a binder was added in an amount of 0.8 mass% based on the solid content, and then granulated and dried by a spray dryer, and held at 1350 ℃ for 5 hours by an electric furnace, followed by main firing.

Then, the carrier core particles are obtained by pulverizing, further classifying and adjusting the particle size, and then classifying the low magnetic products by magnetic separation. The particle diameter of the carrier core particle 1 was 35 μm.

(preparation of core Material-coating resin)

To a 0.3 mass% aqueous solution of sodium benzenesulfonate, cyclohexyl methacrylate and methyl methacrylate were added in a mass ratio of 5:5 "(copolymerization ratio), and potassium persulfate was added in an amount of 0.5 mass% of the total amount of the monomers to carry out emulsion polymerization, followed by drying by spray drying to prepare a" coating material ". The weight average molecular weight of the obtained coating material 1 was 50 ten thousand.

(preparation of the support)

In a high-speed stirring mixer with a horizontal stirring blade, 100 parts by mass of the prepared "carrier core particles" and 4.5 parts by mass of the "coating material" as core particles were charged, and mixed and stirred at 22 ℃ for 15 minutes at a peripheral speed of 8m/sec of a horizontal rotating blade, and then mixed at 120 ℃ for 50 minutes to coat the surfaces of the core particles with the coating material by the action of a mechanical impact force (mechanochemical method), thereby producing "carriers".

Preparation of developing agent

The toner particles and the carrier particles prepared in the above manner were mixed so that the toner concentration was 7 mass%, to prepare a developer. The mixture was mixed at 25 ℃ for 30 minutes using a V-type mixer (manufactured by TO KUJU, Co., Ltd.).

Evaluation

Using a commercially available color multifunction peripheral "bizhub PRESS (registered trademark) C1070" (manufactured by Konika Minuda), a high-grade paper (65 g/m in weight in square meter) of A4 edition was coated under a normal temperature and humidity environment (20 ℃ C., 50% RH)²) In the above, 5 ten thousand prints were made to form a band-like solid image having a coverage of 5% as a test image. Then, the sample was transferred to a high-temperature and high-humidity environment (temperature 30 ℃ C., humidity 80% RH) and measured for 5 ten thousand timesThe test image was printed to form a band-like solid image having a coverage of 5%.

After printing, the following evaluations were performed.

(electric quantity)

The charge amount of the toner in this sample was measured by a charge amount measuring device "BLOW-OFF TB-200" (manufactured by Toshiba Co., Ltd.). A400-mesh stainless steel screen was attached to the apparatus under a blowing pressure of 0.5kgf/cm²Nitrogen was blown under the conditions of (1) for 10 seconds. The charge amount (. mu.C/g) was calculated by dividing the measured charge by the flying mass of the toner.

(dot reproducibility)

The gradation pattern at the gradation ratio 24 stage was output, and the graininess thereof was evaluated to evaluate the dot reproducibility. Specifically, fourier transform processing is performed on the gradation pattern by correcting the CCD read value in consideration of mtf (modulation Transfer function), and the GI value (gain Index) corresponding to the human luminance Factor (luminance Factor) is measured, and the maximum Graininess (GI value) is obtained in the gradation pattern at 24 steps. The smaller the GI value, the better, and the smaller the GI value, the less grainy feeling of the image is expressed. The GI value is a value described in Japan society of image science 39(2), 84-93 (2000). The graininess of the gradation pattern in the image was evaluated according to the following evaluation criteria.

O: the maximum GI value was 0.170 or less, which is a good level

And (delta): the maximum GI value was more than 0.170 and 0.180 or less, which is a good level

X: maximum GI value greater than 0.180, which is a problematic level

(color reproducibility)

The test chart for measuring the color gamut was outputted in the default mode using the "bizhub PRESS (registered trademark) C1070" (manufactured by konica minolta co., ltd.), and the outputted test chart for measuring the color gamut was measured by a "fluorescence densitometer FD-7 (manufactured by konica minolta co., ltd.). The color gamut measurement was performed under the following conditions.

Measurement conditions

Light source: d50 light source

Observation visual field: 2 degree

Density: ANSI T

White standard: abs

A filter: UV Cut

Measurement mode: reflectance ratio

Speech: japanese language

In the evaluation of the color gamut measurement, solid images (2cm × 2cm) of yellow single color (Y), magenta single color (M), cyan single color (C), red (R), blue (B), and green (G) were prepared. The gamut composed of Y/M/C/R/G/B based on these solid images is in a^*-b^*Expressed in coordinates, and the area thereof was measured as a color gamut area. The color gamut of the image prepared with the electrostatic latent image developing toner 18 of the comparative example was evaluated as a relative value with the color gamut area being 100.

O: the color reproducibility exceeded 110, which was a good level

And (delta): the color reproducibility exceeded 100 and was 110 or less, which was a good level

X: color reproducibility of 100 or less, which is a level causing problems

(Low temperature fixability)

The "bizhub PRESS (registered trademark) C1070" (manufactured by konica minolta co., ltd.) was modified so that the surface temperature of the heating roller in the fixing device could be changed in 5 ℃ scale within a range of 140 to 200 ℃, and the high-grade paper (having a square meter weight of 64 g/m) having a size of a4 under a normal temperature and humidity (temperature of 20 ℃, humidity of 55% RH) environment was modified²) Solid image of 2cm × 2cm fixed thereon (toner adhesion amount 3.0 mg/cm)²) The fixing test of (2) was repeated while changing the set fixing temperature (surface temperature of the heating roller) so as to increase the scale of 5 ℃ as in 120 ℃ and 135 ℃. The solid image obtained in each fixing experiment was folded from the center to 2 portions, and the peeling property of the image was visually observed, and in the fixing experiment in which no image was peeled, the lowest fixing temperature was set as the fixing lower limit temperature.

O: the lower fixing limit temperature is 140 ℃ or lower, which is a good level

And (delta): the lower fixing limit temperature is more than 140 ℃ and 150 ℃ or less, which is a good level

X: the lower fixing limit temperature exceeds 150 ℃, which is a problematic level

The results are shown in Table I.

[ Table 1]

As is apparent from table I, the toner for electrostatic latent image development of the present invention is a toner for electrostatic latent image development that can suppress image quality degradation in environmental changes, and has excellent dot reproducibility even under high temperature and high humidity, and excellent color reproducibility and low temperature fixability.

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